Substituted Pyridopyrazines with a Herbicidal Action

ABSTRACT

Substituted pyrazines of the formula I 
     
       
         
         
             
             
         
       
     
     in which the variables are defined according to the description, their agriculturally suitable salts, processes and intermediates for preparing the pyrazines of the formula I, compositions comprising them and their use as herbicides, i.e. for controlling harmful plants, and also a method for controlling unwanted vegetation which comprises allowing a herbicidally effective amount of at least one pyrazine compound of the formula I to act on plants, their seed and/or their habitat.

The present invention relates to substituted pyrazines of the formula I

in which the variables have the following meaning:

-   R¹ is O—R^(A), or S(O)_(n)—R^(A) or OS(O)_(n)—R^(A);     -   R^(A) is hydrogen, C₁-C₄-alkyl, Z—C₃-C₆-cycloalkyl,         C₁-C₄-haloalkyl, C₂-C₆-alkenyl, Z—C₃-C₆-cycloalkenyl,         C₂-C₆-alkynyl, Z—C(═O)—R^(a), Z—P(═O)(R^(a))₂, a 3- to         7-membered monocyclic or 9- or 10-membered bicyclic saturated,         unsaturated or aromatic heterocycle which contains 1, 2, 3 or 4         heteroatoms selected from the group consisting of O, N and S,         which may be partially or fully substituted by groups R^(a)         and/or R^(b) and which is attached via carbon or nitrogen,         -   R^(a) is hydrogen, OH, C₁-C₈-alkyl, C₁-C₄-haloalkyl,             Z—C₃-C₆-cycloalkyl, C₂-C₈-alkenyl, Z—C₅-C₆-cycloalkenyl,             C₂-C₈-alkynyl, Z—C₁-C₆-alkoxy, Z—C₁-C₄-haloalkoxy,             Z—C₃-C₈-alkenyloxy,             -   Z—C₃-C₈-alkynyloxy, NR^(i)R^(ii), C₁-C₆-alkylsulfonyl,                 Z-(tri-C₁-C₄-alkyl)silyl, Z-phenyl, Z-phenoxy,                 Z-phenylamino or a 5- or 6-membered monocyclic or 9- or                 10-membered bicyclic heterocycle which contains 1, 2, 3                 or 4 heteroatoms selected from the group consisting of                 O, N and S, where the cyclic groups are unsubstituted or                 substituted by 1, 2, 3 or 4 groups R^(b);         -   R^(i), R^(ii) independently of one another are hydrogen,             C₁-C₈-alkyl, C₁-C₄-halo-alkyl, C₃-C₈-alkenyl, C₃-C₈-alkynyl,             Z—C₃-C₆-cycloalkyl, Z—C₁-C₈-alkoxy, Z—C₁-C₈-haloalkoxy;             -   R^(i) and R^(ii) together with the nitrogen atom to                 which they are attached may also form a 5- or 6-membered                 monocyclic or 9- or 10-membered bicyclic heterocycle                 which contains 1, 2, 3 or 4 heteroatoms selected from                 the group consisting of O, N and S;         -   Z is a covalent bond or C₁-C₄-alkylene;     -   n is 0, 1 or 2; -   R² is phenyl, naphthyl or a 5- or 6-membered monocyclic or 9- or     10-membered bicyclic aromatic heterocycle which contains 1, 2, 3 or     4 heteroatoms selected from the group consisting of O, N and S,     where the cyclic groups are unsubstituted or substituted by 1, 2, 3     or 4 groups R^(b);     -   R^(b) independently of one another are Z—CN, Z—OH, Z—NO₂,         Z-halogen, C₁-C₈-alkyl, C₁-C₄-haloalkyl, C₂-C₈-alkenyl,         C₂-C₈-alkynyl, Z—C₁-C₈-alkoxy, Z—C₁-C₈-haloalkoxy,         Z—C₃-C₁₀-cycloalkyl, O—Z—C₃-C₁₀-cycloalkyl, Z—C(═O)—R^(a),         NR^(i)R^(ii), Z-(tri-C₁-C₄-alkyl)silyl, Z-phenyl and         S(O)_(n)R^(b),         -   where R^(bb) is C₁-C₈-alkyl or C₁-C₆-haloalkyl and         -   n is 0, 1 or 2;     -   R^(b1), R^(b2) are one of the groups mentioned for R^(b);     -   R^(b), R^(b1), R^(b2) independently of one another together with         the group R^(b), R^(b1) or R^(b2) attached to the adjacent         carbon atom may also form a five- or six-membered saturated or         partially or fully unsaturated ring which, in addition to carbon         atoms, may contain 1, 2 or 3 heteroatoms selected from the group         consisting of O, N and S; -   X is O, S or N—R³;     -   R³ is hydrogen, C₁-C₆-alkyl, C₁-C₄-haloalkyl, C₂-C₆-alkenyl,         C₃-C₆-alkynyl, Z—C₃-C₁₀-cycloalkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl,         C₁-C₆-cyanoalkyl, Z-phenyl, Z—C(═O)—R^(a2) or         tri-C₁-C₄-alkylsilyl;         -   R^(a2) is C₁-C₆-alkyl, C₁-C₄-haloalkyl, Z—C₁-C₆-alkoxy,             Z—C₁-C₄-haloalkoxy or NR^(i)R^(ii);             where in the groups R^(A), R², R³ and their subsubtituents,             the carbon chains and/or the cyclic groups may be partially             or fully substituted by groups R^(a),             or a N-oxide or an agriculturally suitable salt thereof;             with the proviso that R¹ is not OR^(A) or OS(O)_(n)—R^(A) if             X is O.

Moreover, the invention relates to processes and intermediates for preparing the pyrazines of the formula I and the N-oxides thereof, the agriculturally usable salts thereof, and also to active compound combinations comprising them, to compositions comprising them and to their use as herbicides, i.e. for controlling harmful plants, and also to a method for controlling unwanted vegetation which comprises allowing a herbicidally effective amount of at least one pyrazine compound of the formula I or of an agriculturally suitable salt of I to act on plants, their seed and/or their habitat.

Further embodiments of the present invention can be found in the claims, the description and the examples. It is to be understood that the features mentioned above and those still to be illustrated below of the subject matter of the invention can be applied not only in the respective given combination but also in other combinations without leaving the scope of the invention.

WO 2008/009908 and WO 2008/071918 describe herbicidal pyrazines; however, their herbicidal action at low application rates and/or their compatibility with crop plants leave scope for improvement.

It is an object of the present invention to provide compounds having herbicidal action. To be provided are in particular active compounds having strong herbicidal action, in particular even at low application rates, whose compatibility with crop plants is sufficient for commercial application.

These and further objects are achieved by the compounds of the formula I defined at the outset and by their N-oxides and also their agriculturally suitable salts.

The compounds according to the invention can be prepared according to standard processes of organic chemistry, for example according to the following synthesis route:

Pyridine carboxylic acids of the formula II can be reacted with compounds of the formula III to give compounds of the formula IV. In the formulae II and III, the variables have the meaning given for formula I. The group R¹ is C₁-C₄-alkoxy, Hal is a halogen atom or another suitable nucleophilic leaving group, such as alkoxy or phenoxy, and SG is a protective group which lowers the reactivity of Y, such as, for example, optionally substituted benzyl.

This reaction is usually carried out at temperatures of from −78° C. to 120° C., preferably from −20° C. to 50° C., in an inert organic solvent in the presence of a base (cf. Greene's Protective Groups in Organic Synthesis, Wiley).

Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, dimethylformamide (DMF) and dimethylacetamide, particularly preferably halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene. It is also possible to use mixtures of the solvents mentioned.

Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides, such as methylmagnesium chloride, and also alkali metal and alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, tributylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines. Preference is given to alkali metal and alkaline earth metal hydroxides, particularly preferably sodium hydroxide. The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvents.

The starting materials are generally reacted with one another in equimolar amounts.

The appropriate acid of the formula V is released from the compounds of the formula IV. This reaction is usually carried out at temperatures of from −78° C. to 120° C., preferably from −20° C. to 50° C., in an inert organic solvent in the presence of a base (cf. Bioorganic and Medicinal Chemistry Letters (2006) vol. 16(3), 718-721).

Suitable solvents are water, alcohols, such as methanol, ethanol and isopropanol, aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, DMF and dimethylacetamide, particularly preferably halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene. It is also possible to use mixtures of the solvents mentioned.

Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides, such as methylmagnesium chloride, and also alkali metal and alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, tributylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines. Preference is given to alkali metal and alkaline earth metal hydroxides, particularly preferably lithium hydroxide. The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvents.

The compounds of the formula V are activated by introducing a leaving group L¹. Suitable leaving groups L¹ are, in general, groups which increase the electrophilicity of the carbonyl group, for example O-alkyl, O-aryl, halides, activated esters or aldehydes (such as, for example, Weinreb amide), in particular pentafluorophenoxy.

This reaction is usually carried out at temperatures of from −78° C. to 120° C., preferably from −20° C. to 50° C., in an inert organic solvent in the presence of a base, such as, for example, triethylamine (cf. J. Agric. and Food Chem. 1994, 42(4), 1019-1025), a catalyst, such as, for example, dicyclohexylcarbodiimide (cf. Egyptian Journal of Chemistry 1994, 37(3), 273-282) or other known coupling agents.

Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, DMF and dimethylacetamide, particularly preferably methylene chloride and toluene. It is also possible to use mixtures of the solvents mentioned.

Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides, such as methylmagnesium chloride, and also alkali metal and alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, tributylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines. Particular preference is given to alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate, calcium carbonate, cesium carbonate and rubidium carbonate. The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvents.

The starting materials are generally reacted with one another in equimolar amounts.

Suitable agents H-L¹ are alcohols, optionally subst. phenols, N,O-dialkyl-hydroxylamine, in particular pentafluorophenol or N,O-dimethylhydroxylamine.

The compounds of the formula VI are reacted with acetic acid derivatives of the formula VII to give the compounds of the formula VIII.

This reaction is usually carried out at temperatures of from −78° C. to 120° C., preferably from −20° C. to 50° C., in an inert organic solvent in the presence of a base or a Lewis acid or a catalyst [cf. Bioorganic & Medicinal Chemistry (2004) vol. 12(6), 1357-1366].

Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chloro-benzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, DMF and dimethylacetamide, particularly preferably acetonitrile and DMF. It is also possible to use mixtures of the solvents mentioned.

Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate, calcium carbonate, cesium carbonate and rubidium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides, such as methylmagnesium chloride, and also alkali metal and alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, tributylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines. Preference is given to alkali metal and alkaline earth metal alkoxides, particularly preferably potassium tert-butoxide.

The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvents.

The starting materials are generally reacted with one another in equimolar amounts.

By removing the protective group, the compounds of the formula IX can be released from the compounds of the formula VIII. The reaction conditions depend on the nature of the protective group SG; the removal of an optionally subst. benzyl group succeeds, for example, using trifluoroacetic acid at temperatures of from −78° C. to 100° C., preferably from −20° C. to 50° C., in an inert organic solvent [cf. Greene's Protective Groups in Organic Synthesis, Wiley].

The introduction of the groups X and Y different from oxygen into the compounds of the formula I or their precursors is carried out using generally known methods.

The compounds of the formula IX and their precursors can be present in two tautomeric forms. The invention relates to both tautomers. For clarity, the description generally mentions only one tautomer.

The compounds of the formula IX can be converted by cyclization into compounds of the formula I. The cyclization succeeds, for example, with sat. sodium chloride solution and an organic solvent at temperatures of from −30° C. to 150° C., preferably from 30° C. to 100° C.

This reaction is usually carried out at temperatures of from −78° C. to 120° C., preferably from −20° C. to 50° C.

Suitable solvents are water, alcohols, such as methanol, ethanol, isopropanol, aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, DMF and dimethylacetamide, particularly preferably halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene. It is also possible to use mixtures of the solvents mentioned.

The sulfurization of the compounds of the formula X is carried out under conditions known per se using a sulfurizing agent [S]; it is usually carried out at temperatures of from 0° C. to 180° C., preferably from 20° C. to 140° C., in an inert organic solvent [cf. Liebigs Ann. Chem., p. 177 (1989)].

Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, and also dimethyl sulfoxide, particularly preferably toluene and tetrahydrofuran. It is also possible to use mixtures of the solvents mentioned.

Suitable sulfurizing agents are, for example, phosphorus pentasulfide or Lawesson's reagent.

The introduction of the groups N—R³ in the compounds of the formula I or X, or of R¹, or R^(A), is carried out under generally known conditions. The compounds of the formula I in which R¹ is a group attached via S can be obtained, for example, via a reaction sequence according to Newman-Kwart starting with chlorothiocarbonyl compounds [cf.: J. Org. Chem., Vol. 59(21), pp. 6318-21 (1994)].

The reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and optionally chromatographic purification of the crude products. Some of the intermediates and end products are obtained in the form of colorless or slightly brownish viscous oils which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, the purification can also be carried out by recrystallization or digestion.

If individual compounds I cannot be obtained by the routes described above, they can be prepared by derivatization of other compounds I.

If the synthesis yields mixtures of isomers, a separation is generally however not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (for example under the action of light, acids or bases). Such conversions may also take place after application, for example in the case of the treatment of plants in the treated plant or in the harmful plant to be controlled.

The organic moieties mentioned for the substituents of the compounds according to the invention are collective terms for individual enumerations of the individual group members. All hydrocarbon chains, such as alkyl, haloalkyl, alkenyl, alkynyl, and the alkyl moieties and alkenyl moieties in alkoxy, haloalkoxy, alkylamino, dialkylamino, N-alkylsulfonylamino, alkenyloxy, alkynyloxy, alkoxyamino, alkylaminosulfonylamino, dialkylaminosulfonylamino, alkenylamino, alkynylamino, N-(alkenyl)-N-(alkyl)amino, N-(alkynyl)-N-(alkyl)amino, N-(alkoxy)-N-(alkyl)amino, N-(alkenyl)-N-(alkoxy)amino or N-(alkynyl)-N-(alkoxy)amino can be straight-chain or branched.

The prefix C_(n)-C_(m)— indicates the respective number of carbons of the hydrocarbon unit. Unless indicated otherwise, halogenated substituents preferably carry one to five identical or different halogen atoms, in particular fluorine atoms or chlorine atoms.

The meaning halogen denotes in each case fluorine, chlorine, bromine or iodine.

Examples of other meanings are:

alkyl and the alkyl moieties for example in alkoxy, alkylamino, dialkylamino, N-alkyl-sulfonylamino, alkylaminosulfonylamino, dialkylaminosulfonylamino, N-(alkenyl)-N-(alkyl)amino, N-(alkynyl)-N-(alkyl)amino, N-(alkoxy)-N-(alkyl)amino: saturated straight-chain or branched hydrocarbon radicals having one or more carbon atoms, for example 1 or 2, 1 to 4 or 1 to 6 carbon atoms, for example C₁-C₆-alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethyl-butyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethyl-propyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl. In one embodiment according to the invention, alkyl denotes small alkyl groups, such as C₁-C₄-alkyl. In another embodiment according to the invention, alkyl denotes relatively large alkyl groups, such as C₅-C₆-alkyl.

Haloalkyl: an alkyl radical as mentioned above, some or all of whose hydrogen atoms are substituted by halogen atoms, such as fluorine, chlorine, bromine and/or iodine, for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoro-methyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoro-ethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl.

Cycloalkyl and the cycloalkyl moieties for example in cycloalkoxy or cycloalkylcarbonyl: monocyclic saturated hydrocarbon groups having three or more carbon atoms, for example 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Alkenyl and the alkenyl moieties for example in alkenylamino, alkenyloxy, N-(alkenyl)-N-(alkyl)amino, N-(alkenyl)-N-(alkoxy)amino: monounsaturated straight-chain or branched hydrocarbon radicals having two or more carbon atoms, for example 2 to 4, 2 to 6 or 3 to 6 carbon atoms, and a double bond in any position, for example C₂-C₆-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl.

Cycloalkenyl: monocyclic monounsaturated hydrocarbon groups having 3 to 6, preferably 5 or 6, carbon ring members, such as cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl, cyclohexen-4-yl.

Alkynyl and the alkynyl moieties for example in alkynyloxy, alkynylamino, N-(alkynyl)-N-(alkyl)amino or N-(alkynyl)-N-(alkoxy)amino: straight-chain or branched hydrocarbon groups having two or more carbon atoms, for example 2 to 4, 2 to 6 or 3 to 6 carbon atoms, and a triple bond in any position, for example C₂-C₆-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl.

Alkoxy: alkyl as defined above which is attached via an oxygen atom, for example methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methyl-propoxy or 1,1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methyl-butoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethyl-propoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methyl-pentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethyl-butoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy.

A 5- or 6-membered heterocycle: a cyclic group which has 5 or 6 ring atoms, 1, 2, 3 or 4 ring atoms being heteroatoms selected from the group consisting of O, S and N, where the cyclic group is saturated, partially unsaturated or aromatic.

The compounds of the formula I may, depending on the substitution pattern, contain one or more further centers of chirality. Accordingly, the compounds according to the invention can be present as pure enantiomers or diastereomers or as enantiomer or diastereomer mixtures. The invention provides both the pure enantiomers or diastereomers and their mixtures.

The compounds of the formula I may also be present in the form of the N-oxides and/or of their agriculturally useful salts, the type of salt generally not being important. Suitable salts are generally the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the herbicidal activity of the compounds I.

Suitable cations are in particular ions of the alkali metals, preferably lithium, sodium or potassium, of the alkaline earth metals, preferably calcium or magnesium, and of the transition metals, preferably manganese, copper, zinc or iron. Another cation that may be used is ammonium, where, if desired, one to four hydrogen atoms may be replaced by C₁-C₄-alkyl, hydroxy-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, hydroxy-C₁-C₄-alkoxy-C₁-C₄-alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropyl-ammonium, tetramethylammonium, tetrabutylammonium, 2-(2-hydroxyeth-1-oxy)eth-1-ylammonium, di(2-hydroxyeth-1-yl)ammonium, trimethylbenzylammonium. Another suitable ammonium cation is the pyridine nitrogen atom of the formula I quaternized by alkylation or arylation. Also suitable are phosphonium ions, sulfonium ions, preferably tri(C₁-C₄-alkyl)sulfonium, or sulfoxonium ions, preferably tri(C₁-C₄-alkyl)sulfoxonium.

Anions of suitable acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and also the anions of C₁-C₄-alkanoic acids, preferably formate, acetate, propionate, butyrate or trifluoroacetate.

With respect to the variables, the particularly preferred embodiments of the intermediates correspond to those of the groups of the formula I.

In a particular embodiment, the variables of the compounds of the formula I have the following meanings, these meanings, both on their own and in combination with one another, being particular embodiments of the compounds of the formula I:

In a first preferred embodiment of the invention, R¹ is O—R^(A).

In a further preferred embodiment of the invention, R¹ is S(O)_(n)—R^(A) where n is preferably 0 or 2, in particular 0.

R^(A) is in particular H, C₁-C₆-alkylcarbonyl, such as C(O)CH₃, C(O)CH₂CH₃, C(O)CH(CH₃)₂ or C(O)C(CH₃)₃; C₁-C₆-cycloalkylcarbonyl, such as cyclopropylcarbonyl, cyclopentylcarbonyl or cyclohexylcarbonyl; C₂-C₆-alkenylcarbonyl, such as C(O)CH═CH₂ or C(O)CH₂CH═CH₂, optionally subst. benzoyl, such as C(O)C₆H₅, C(O)[2-CH₃—C₆H₄], C(O)[4-CH₃—C₆H₄], C(O)[2-F—C₆H₄], C(O)[4-F—C₆H₄], or optionally subst. heteroaryl, such as pyridine, which is attached via a carbonyl group.

In a further preferred aspect, R^(A) is H, C₁-C₆-alkyl, optionally subst. phenyl, di-C₁-C₆-alkylaminocarbonyl, C₁-C₆-alkylcarbonyl or benzoyl.

Particularly preferably, R^(A) is H or C₁-C₆-alkylcarbonyl.

In a further preferred embodiment of the invention, R^(A) is a 5- or 6-membered heterocycle optionally substituted by R^(b) as defined above, which preferably has either 1, 2, 3 or 4 nitrogen atoms or 1 oxygen or 1 sulfur atom and optionally 1 or 2 nitrogen atoms as ring members and which is unsubstituted or may have 1 or 2 substituents selected from R^(b). Preference is given to saturated or unsaturated groups attached via nitrogen, such as, for example:

Heteroaromatic groups: pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl and thiazol-5-yl;

In another aspect, R^(A) is a heteroaromatic group attached via carbon, such as pyrazol-3-yl, imidazol-5-yl, oxazol-2-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyridazin-4-yl, pyrazin-2-yl, [1H]-tetrazol-5-yl and [2H]-tetrazol-5-yl, where each of the heterocycles mentioned here in an exemplary manner may have 1 or 2 substituents selected from R^(b). Preferred groups R^(b) are in particular F, Cl, CN, NO₂, CH₃, C₂H₅, OCH₃, OC₂H₅, OCHF₂, OCF₃ and CF₃.

In a further preferred aspect, R² is phenyl which is unsubstituted or partially or fully substituted by groups R^(b). Particular preference is given to compounds in which a group R^(b) is located in the ortho-position. Such compounds of the formula I are described by the formula I.A:

In formula I.A, the index n is an integer from zero to four, preferably 0, 1 or 2, in particular 0 or 1. R⁵ and R⁶ are groups R^(b) as defined at the outset, preferably halogen, NO₂, C₁-C₄-alkyl, C₁-C₂-haloalkyl and C₁-C₄-alkoxy. One group R⁶ is preferably located in position 5.

In a preferred embodiment, X is S.

In a further embodiment, X is NR³. The two groups R³ may be identical or different.

R³ is preferably H, C₁-C₆-alkyl, such as CH₃, C₂H₅, n-C₃H₇, CH(CH₃)₂, n-C₃H₉, or C(CH₃)₃; C₃-C₆-cycloalkyl-C₁-C₄-alkyl, such as cyclopropylmethyl, C₃-C₆-alkenyl, such as CH₂CH═CH₂, CH₂C(CH₃)═CH₂, CH₂CH₂H═CH₂, CH₂CH₂C(CH₃)—CH₂, CH₂CH₂CH₂CH═CH₂, CH₂CH₂CH₂C(CH₃)═CH₂, or optionally subst. phenyl, such as C₆H₅, 4-CH₃—C₆H₄, 4-F—C₆H₄ or S(O)_(n)—R^(N), where R^(N) is C₁-C₆-haloalkyl, such as CH₂CF₃, CH₂CHF₂. R³ is particularly preferably not hydrogen. Especially preferably, R³ is C₁-C₆-haloalkyl, such as CH₂CF₃ or CH₂CHF₂.

A further embodiment relates to compounds of the formula I in which R^(b1) and R^(b2) are each hydrogen.

A further embodiment relates to the N-oxides of the compounds of the formula I.

A further embodiment relates to salts of the compounds of the formula I, in particular those which are obtainable by quaternization of at least one pyrazine nitrogen atom, which may preferably take place by alkylation or arylation of the compounds of the formula I. Preferred salts of the compounds are thus the N-alkyl salts, in particular the N-methyl salts, and the N-phenyl salts.

In particular with a view to their use, preference is given to the compounds of the formula I compiled in the tables below, which compounds correspond to the formula I.A, in which R^(b1) and R^(b2) are each hydrogen (formula I.AA).

The groups mentioned for a substituent in the tables are furthermore per se, independently of the combination in which they are mentioned, a particularly preferred aspect of the substituent in question.

Table 1

Compounds of the formula I in which X is O and R³ is H and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to a row A-1 to A-48 of table A

Table 2

Compounds of the formula I in which X is O and R³ is CH₃ and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to a row A-1 to A-48 of table A

Table 3

Compounds of the formula I in which X is O and R³ is C₂H₅ and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to a row A-1 to A-48 of table A

Table 4

Compounds of the formula I in which X is O and R³ is n-C₃H₇ and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to a row A-1 to A-48 of table A

Table 5

Compounds of the formula I in which X is O and R³ is CH(CH₃)₂ and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to a row A-1 to A-48 of table A

Table 6

Compounds of the formula I in which X is O and R³ is n-C₄H₉ and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to a row A-1 to A-48 of table A

Table 7

Compounds of the formula I in which X is O and R³ is CH₂CH═CH₂ and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to a row A-1 to A-48 of table A

Table 8

Compounds of the formula I in which X is O and R³ is CH₂C≡CH and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to a row A-1 to A-48 of table A

Table 9

Compounds of the formula I in which X is O and R³ is CH₂CN and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to a row A-1 to A-48 of table A

Table 10

Compounds of the formula I in which X is O and R³ is CH₂CF₃ and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to a row A-1 to A-48 of table A

Table 11

Compounds of the formula I in which X is O and R³ is CH₂CHF₂ and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to a row A-1 to A-48 of table A

Table 12

Compounds of the formula I in which X is O and R³ is CH₂C₆H₅ and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to a row A-1 to A-48 of table A

Table 13

Compounds of the formula I in which X is S and R³ is H and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to one row of table A

Table 14

Compounds of the formula I in which X is S and R³ is CH₃ and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to one row of table A

Table 15

Compounds of the formula I in which X is S and R³ is C₂H₅ and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to one row of table A

Table 16

Compounds of the formula I in which X is S and R³ is n-C₃H₇ and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to one row of table A

Table 17

Compounds of the formula I in which X is S and R³ is CH(CH₃)₂ and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to one row of table A

Table 18

Compounds of the formula I in which X is S and R³ is n-C₄H₉ and the combination of R¹, R⁵ and (R⁶), for a compound corresponds in each case to one row of table A

Table 19

Compounds of the formula I in which X is S and R³ is CH₂CH═CH₂ and the combination of R¹, R⁵ and (R⁶), for a compound corresponds in each case to one row of table A

Table 20

Compounds of the formula I in which X is S and R³ is CH₂C≡CH and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to one row of table A

Table 21

Compounds of the formula I in which X is S and R³ is CH₂CN and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to one row of table A

Table 22

Compounds of the formula I in which X is S and R³ is CH₂CF₃ and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to one row of table A

Table 23

Compounds of the formula I in which X is S and R³ is CH₂CHF₂ and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to one row of table A

Table 24

Compounds of the formula I in which X is S and R³ is CH₂C₆H₅ and the combination of R¹, R⁵ and (R⁶)_(n) for a compound corresponds in each case to one row of table A

TABLE A Compounds of the formula I which correspond to the formula I.A, in which R^(b1) and R^(b2) are each hydrogen (formula I.AA) I.AA

No. R¹ R⁵ (R⁶)_(n) A-1 SH CF₃ — A-2 SH CF₃ 4-F A-3 SH CF₃ 5-F A-4 SH CF₃ 5-Cl A-5 SCH₃ CF₃ — A-6 SCH₃ CF₃ 4-F A-7 SCH₃ CF₃ 5-F A-8 SCH₃ CF₃ 5-Cl A-9 SC₆H₅ CF₃ — A-10 SC₆H₅ CF₃ 4-F A-11 SC₆H₅ CF₃ 5-F A-12 SC₆H₅ CF₃ 5-Cl A-13 SC(O)N(CH₃)₂ CF₃ — A-14 SC(O)N(CH₃)₂ CF₃ 4-F A-15 SC(O)N(CH₃)₂ CF₃ 5-F A-16 SC(O)N(CH₃)₂ CF₃ 5-Cl A-17 SC(O)CH₃ CF₃ — A-18 SC(O)CH₃ CF₃ 4-F A-19 SC(O)CH₃ CF₃ 5-F A-20 SC(O)CH₃ CF₃ 5-Cl A-21 SC(O)CH(CH₃)₂ CF₃ — A-22 SC(O)CH(CH₃)₂ CF₃ 4-F A-23 SC(O)CH(CH₃)₂ CF₃ 5-F A-24 SC(O)CH(CH₃)₂ CF₃ 5-Cl A-25 SC(O)C(CH₃)₃ CF₃ — A-26 SC(O)C(CH₃)₃ CF₃ 4-F A-27 SC(O)C(CH₃)₃ CF₃ 5-F A-28 SC(O)C(CH₃)₃ CF₃ 5-Cl A-29 SC(O)C₆H₅ CF₃ — A-30 SC(O)C₆H₅ CF₃ 4-F A-31 SC(O)C₆H₅ CF₃ 5-F A-32 SC(O)C₆H₅ CF₃ 5-Cl A-33 S(O)CH₃ CF₃ — A-34 S(O)CH₃ CF₃ 4-F A-35 S(O)CH₃ CF₃ 5-F A-36 S(O)CH₃ CF₃ 5-Cl A-37 S(O)C₆H₅ CF₃ — A-38 S(O)C₆H₅ CF₃ 4-F A-39 S(O)C₆H₅ CF₃ 5-F A-40 S(O)C₆H₅ CF₃ 5-Cl A-41 S(O)₂CH₃ CF₃ — A-42 S(O)₂CH₃ CF₃ 4-F A-43 S(O)₂CH₃ CF₃ 5-F A-44 S(O)₂CH₃ CF₃ 5-Cl A-45 S(O)₂C₆H₅ CF₃ — A-46 S(O)₂C₆H₅ CF₃ 4-F A-47 S(O)₂C₆H₅ CF₃ 5-F A-48 S(O)₂C₆H₅ CF₃ 5-Cl A-49 OH Br — A-50 OCH₃ Br — A-51 OC(O)CH₃ Br — A-52 OC(O)CH₂CH₃ Br — A-53 OC(O)CH(CH₃)₂ Br — A-54 OC(O)C(CH₃)₃ Br — A-55 OC(O)c-C₃H₅ Br — A-56 OC(O)C₆H₅ Br — A-57 OC(O)CH₂C₆H₅ Br — A-58 OC(O)CH₂Cl Br — A-59 OC(O)CF₃ Br — A-60 OC(O)CH₂OCH₃ Br — A-61 OC(O)N(CH₃)₂ Br — A-62 OC(O)OCH₂CH₃ Br — A-63 OH Cl — A-64 OCH₃ Cl — A-65 OC(O)CH₃ Cl — A-66 OC(O)CH₂CH₃ Cl — A-67 OC(O)CH(CH₃)₂ Cl — A-68 OC(O)C(CH₃)₃ Cl — A-69 OC(O)c-C₃H₅ Cl — A-70 OC(O)C₆H₅ Cl — A-71 OC(O)CH₂C₆H₅ Cl — A-72 OC(O)CH₂Cl Cl — A-73 OC(O)CF₃ Cl — A-74 OC(O)CH₂OCH₃ Cl — A-75 OC(O)N(CH₃)₂ Cl — A-76 OC(O)OCH₂CH₃ Cl — A-77 OH F — A-78 OCH₃ F — A-79 OC(O)CH₃ F — A-80 OC(O)CH₂CH₃ F — A-81 OC(O)CH(CH₃)₂ F — A-82 OC(O)C(CH₃)₃ F — A-83 OC(O)c-C₃H₅ F — A-84 OC(O)C₆H₅ F — A-85 OC(O)CH₂C₆H₅ F — A-86 OC(O)CH₂Cl F — A-87 OC(O)CF₃ F — A-88 OC(O)CH₂OCH₃ F — A-89 OC(O)N(CH₃)₂ F — A-90 OC(O)OCH₂CH₃ F — A-91 OH NO₂ — A-92 OCH₃ NO₂ — A-93 OC(O)CH₃ NO₂ — A-94 OC(O)CH₂CH₃ NO₂ — A-95 OC(O)CH(CH₃)₂ NO₂ — A-96 OC(O)C(CH₃)₃ NO₂ — A-97 OC(O)c-C₃H₅ NO₂ — A-98 OC(O)C₆H₅ NO₂ — A-99 OC(O)CH₂C₆H₅ NO₂ — A-100 OC(O)CH₂Cl NO₂ — A-101 OC(O)CF₃ NO₂ — A-102 OC(O)CH₂OCH₃ NO₂ — A-103 OC(O)N(CH₃)₂ NO₂ — A-104 OC(O)OCH₂CH₃ NO₂ — A-105 OH CN — A-106 OCH₃ CN — A-107 OC(O)CH₃ CN — A-108 OC(O)CH₂CH₃ CN — A-109 OC(O)CH(CH₃)₂ CN — A-110 OC(O)C(CH₃)₃ CN — A-111 OC(O)c-C₃H₅ CN — A-112 OC(O)C₆H₅ CN — A-113 OC(O)CH₂C₆H₅ CN — A-114 OC(O)CH₂Cl CN — A-115 OC(O)CF₃ CN — A-116 OC(O)CH₂OCH₃ CN — A-117 OC(O)N(CH₃)₂ CN — A-118 OC(O)OCH₂CH₃ CN — A-119 OH CH₃ — A-120 OCH₃ CH₃ — A-121 OC(O)CH₃ CH₃ — A-122 OC(O)CH₂CH₃ CH₃ — A-123 OC(O)CH(CH₃)₂ CH₃ — A-124 OC(O)C(CH₃)₃ CH₃ — A-125 OC(O)c-C₃H₅ CH₃ — A-126 OC(O)C₆H₅ CH₃ — A-127 OC(O)CH₂C₆H₅ CH₃ — A-128 OC(O)CH₂Cl CH₃ — A-129 OC(O)CF₃ CH₃ — A-130 OC(O)CH₂OCH₃ CH₃ — A-131 OC(O)N(CH₃)₂ CH₃ — A-132 OC(O)OCH₂CH₃ CH₃ — A-133 OH OCH₃ — A-134 OCH₃ OCH₃ — A-135 OC(O)CH₃ OCH₃ — A-136 OC(O)CH₂CH₃ OCH₃ — A-137 OC(O)CH(CH₃)₂ OCH₃ — A-138 OC(O)C(CH₃)₃ OCH₃ — A-139 OC(O)c-C₃H₅ OCH₃ — A-140 OC(O)C₆H₅ OCH₃ — A-141 OC(O)CH₂C₆H₅ OCH₃ — A-142 OC(O)CH₂Cl OCH₃ — A-143 OC(O)CF₃ OCH₃ — A-144 OC(O)CH₂OCH₃ OCH₃ — A-145 OC(O)N(CH₃)₂ OCH₃ — A-146 OC(O)OCH₂CH₃ OCH₃ — A-147 OH CHF₂ — A-148 OCH₃ CHF₂ — A-149 OC(O)CH₃ CHF₂ — A-150 OC(O)CH₂CH₃ CHF₂ — A-151 OC(O)CH(CH₃)₂ CHF₂ — A-152 OC(O)C(CH₃)₃ CHF₂ — A-153 OC(O)c-C₃H₅ CHF₂ — A-154 OC(O)C₆H₅ CHF₂ — A-155 OC(O)CH₂C₆H₅ CHF₂ — A-156 OC(O)CH₂Cl CHF₂ — A-157 OC(O)CF₃ CHF₂ — A-158 OC(O)CH₂OCH₃ CHF₂ — A-159 OC(O)N(CH₃)₂ CHF₂ — A-160 OC(O)OCH₂CH₃ CHF₂ — A-161 OH CF₃ — A-162 OCH₃ CF₃ — A-163 OC(O)CH₃ CF₃ — A-164 OC(O)CH₂CH₃ CF₃ — A-165 OC(O)CH(CH₃)₂ CF₃ — A-166 OC(O)C(CH₃)₃ CF₃ — A-167 OC(O)c-C₃H₅ CF₃ — A-168 OC(O)C₆H₅ CF₃ — A-169 OC(O)CH₂C₆H₅ CF₃ — A-170 OC(O)CH₂Cl CF₃ — A-171 OC(O)CF₃ CF₃ — A-172 OC(O)CH₂OCH₃ CF₃ — A-173 OC(O)N(CH₃)₂ CF₃ — A-174 OC(O)OCH₂CH₃ CF₃ — A-175 OH OCHF₂ — A-176 OCH₃ OCHF₂ — A-177 OC(O)CH₃ OCHF₂ — A-178 OC(O)CH₂CH₃ OCHF₂ — A-179 OC(O)CH(CH₃)₂ OCHF₂ — A-180 OC(O)C(CH₃)₃ OCHF₂ — A-181 OC(O)c-C₃H₅ OCHF₂ — A-182 OC(O)C₆H₅ OCHF₂ — A-183 OC(O)CH₂C₆H₅ OCHF₂ — A-184 OC(O)CH₂Cl OCHF₂ — A-185 OC(O)CF₃ OCHF₂ — A-186 OC(O)CH₂OCH₃ OCHF₂ — A-187 OC(O)N(CH₃)₂ OCHF₂ — A-188 OC(O)OCH₂CH₃ OCHF₂ — A-189 OH OCF₃ — A-190 OCH₃ OCF₃ — A-191 OC(O)CH₃ OCF₃ — A-192 OC(O)CH₂CH₃ OCF₃ — A-193 OC(O)CH(CH₃)₂ OCF₃ — A-194 OC(O)C(CH₃)₃ OCF₃ — A-195 OC(O)c-C₃H₅ OCF₃ — A-196 OC(O)C₆H₅ OCF₃ — A-197 OC(O)CH₂C₆H₅ OCF₃ — A-198 OC(O)CH₂Cl OCF₃ — A-199 OC(O)CF₃ OCF₃ — A-200 OC(O)CH₂OCH₃ OCF₃ — A-201 OC(O)N(CH₃)₂ OCF₃ — A-202 OC(O)OCH₂CH₃ OCF₃ — A-203 OH Cl 4-Cl A-204 OCH₃ Cl 4-Cl A-205 OC(O)CH₃ Cl 4-Cl A-206 OC(O)CH₂CH₃ Cl 4-Cl A-207 OC(O)CH(CH₃)₂ Cl 4-Cl A-208 OC(O)C(CH₃)₃ Cl 4-Cl A-209 OC(O)c-C₃H₅ Cl 4-Cl A-210 OC(O)C₆H₅ Cl 4-Cl A-211 OC(O)CH₂C₆H₅ Cl 4-Cl A-212 OC(O)CH₂Cl Cl 4-Cl A-213 OC(O)CF₃ Cl 4-Cl A-214 OC(O)CH₂OCH₃ Cl 4-Cl A-215 OC(O)N(CH₃)₂ Cl 4-Cl A-216 OC(O)OCH₂CH₃ Cl 4-Cl A-217 OH Cl 4-F A-218 OCH₃ Cl 4-F A-219 OC(O)CH₃ Cl 4-F A-220 OC(O)CH₂CH₃ Cl 4-F A-221 OC(O)CH(CH₃)₂ Cl 4-F A-222 OC(O)C(CH₃)₃ Cl 4-F A-223 OC(O)c-C₃H₅ Cl 4-F A-224 OC(O)C₆H₅ Cl 4-F A-225 OC(O)CH₂C₆H₅ Cl 4-F A-226 OC(O)CH₂Cl Cl 4-F A-227 OC(O)CF₃ Cl 4-F A-228 OC(O)CH₂OCH₃ Cl 4-F A-229 OC(O)N(CH₃)₂ Cl 4-F A-230 OC(O)OCH₂CH₃ Cl 4-F A-231 OH F 4-F A-232 OCH₃ F 4-F A-233 OC(O)CH₃ F 4-F A-234 OC(O)CH₂CH₃ F 4-F A-235 OC(O)CH(CH₃)₂ F 4-F A-236 OC(O)C(CH₃)₃ F 4-F A-237 OC(O)c-C₃H₅ F 4-F A-238 OC(O)C₆H₅ F 4-F A-239 OC(O)CH₂C₆H₅ F 4-F A-240 OC(O)CH₂Cl F 4-F A-241 OC(O)CF₃ F 4-F A-242 OC(O)CH₂OCH₃ F 4-F A-243 OC(O)N(CH₃)₂ F 4-F A-244 OC(O)OCH₂CH₃ F 4-F A-245 OH NO₂ 4-F A-246 OCH₃ NO₂ 4-F A-247 OC(O)CH₃ NO₂ 4-F A-248 OC(O)CH₂CH₃ NO₂ 4-F A-249 OC(O)CH(CH₃)₂ NO₂ 4-F A-250 OC(O)C(CH₃)₃ NO₂ 4-F A-251 OC(O)c-C₃H₅ NO₂ 4-F A-252 OC(O)C₆H₅ NO₂ 4-F A-253 OC(O)CH₂C₆H₅ NO₂ 4-F A-254 OC(O)CH₂Cl NO₂ 4-F A-255 OC(O)CF₃ NO₂ 4-F A-256 OC(O)CH₂OCH₃ NO₂ 4-F A-257 OC(O)N(CH₃)₂ NO₂ 4-F A-258 OC(O)OCH₂CH₃ NO₂ 4-F A-259 OH CH₃ 4-F A-260 OCH₃ CH₃ 4-F A-261 OC(O)CH₃ CH₃ 4-F A-262 OC(O)CH₂CH₃ CH₃ 4-F A-263 OC(O)CH(CH₃)₂ CH₃ 4-F A-264 OC(O)C(CH₃)₃ CH₃ 4-F A-265 OC(O)c-C₃H₅ CH₃ 4-F A-266 OC(O)C₆H₅ CH₃ 4-F A-267 OC(O)CH₂C₆H₅ CH₃ 4-F A-268 OC(O)CH₂Cl CH₃ 4-F A-269 OC(O)CF₃ CH₃ 4-F A-270 OC(O)CH₂OCH₃ CH₃ 4-F A-271 OC(O)N(CH₃)₂ CH₃ 4-F A-272 OC(O)OCH₂CH₃ CH₃ 4-F A-273 OH OCH₃ 4-F A-274 OCH₃ OCH₃ 4-F A-275 OC(O)CH₃ OCH₃ 4-F A-276 OC(O)CH₂CH₃ OCH₃ 4-F A-277 OC(O)CH(CH₃)₂ OCH₃ 4-F A-278 OC(O)C(CH₃)₃ OCH₃ 4-F A-279 OC(O)c-C₃H₅ OCH₃ 4-F A-280 OC(O)C₆H₅ OCH₃ 4-F A-281 OC(O)CH₂C₆H₅ OCH₃ 4-F A-282 OC(O)CH₂Cl OCH₃ 4-F A-283 OC(O)CF₃ OCH₃ 4-F A-284 OC(O)CH₂OCH₃ OCH₃ 4-F A-285 OC(O)N(CH₃)₂ OCH₃ 4-F A-286 OC(O)OCH₂CH₃ OCH₃ 4-F A-287 OH CHF₂ 4-F A-288 OCH₃ CHF₂ 4-F A-289 OC(O)CH₃ CHF₂ 4-F A-290 OC(O)CH₂CH₃ CHF₂ 4-F A-291 OC(O)CH(CH₃)₂ CHF₂ 4-F A-292 OC(O)C(CH₃)₃ CHF₂ 4-F A-293 OC(O)c-C₃H₅ CHF₂ 4-F A-294 OC(O)C₆H₅ CHF₂ 4-F A-295 OC(O)CH₂C₆H₅ CHF₂ 4-F A-296 OC(O)CH₂Cl CHF₂ 4-F A-297 OC(O)CF₃ CHF₂ 4-F A-298 OC(O)CH₂OCH₃ CHF₂ 4-F A-299 OC(O)N(CH₃)₂ CHF₂ 4-F A-300 OC(O)OCH₂CH₃ CHF₂ 4-F A-301 OH CF₃ 4-F A-302 OCH₃ CF₃ 4-F A-303 OC(O)CH₃ CF₃ 4-F A-304 OC(O)CH₂CH₃ CF₃ 4-F A-305 OC(O)CH(CH₃)₂ CF₃ 4-F A-306 OC(O)C(CH₃)₃ CF₃ 4-F A-307 OC(O)c-C₃H₅ CF₃ 4-F A-308 OC(O)C₆H₅ CF₃ 4-F A-309 OC(O)CH₂C₆H₅ CF₃ 4-F A-310 OC(O)CH₂Cl CF₃ 4-F A-311 OC(O)CF₃ CF₃ 4-F A-312 OC(O)CH₂OCH₃ CF₃ 4-F A-313 OC(O)OCH₂CH₃ CF₃ 4-F A-314 OC(O)N(CH₃)₂ CF₃ 4-F A-315 OH OCHF₂ 4-F A-316 OCH₃ OCHF₂ 4-F A-317 OC(O)CH₃ OCHF₂ 4-F A-318 OC(O)CH₂CH₃ OCHF₂ 4-F A-319 OC(O)CH(CH₃)₂ OCHF₂ 4-F A-320 OC(O)C(CH₃)₃ OCHF₂ 4-F A-321 OC(O)c-C₃H₅ OCHF₂ 4-F A-322 OC(O)C₆H₅ OCHF₂ 4-F A-323 OC(O)CH₂C₆H₅ OCHF₂ 4-F A-324 OC(O)CH₂Cl OCHF₂ 4-F A-325 OC(O)CF₃ OCHF₂ 4-F A-326 OC(O)CH₂OCH₃ OCHF₂ 4-F A-327 OC(O)N(CH₃)₂ OCHF₂ 4-F A-328 OC(O)OCH₂CH₃ OCHF₂ 4-F A-329 OH OCF₃ 4-F A-330 OCH₃ OCF₃ 4-F A-331 OC(O)CH₃ OCF₃ 4-F A-332 OC(O)CH₂CH₃ OCF₃ 4-F A-333 OC(O)CH(CH₃)₂ OCF₃ 4-F A-334 OC(O)C(CH₃)₃ OCF₃ 4-F A-335 OC(O)c-C₃H₅ OCF₃ 4-F A-336 OC(O)C₆H₅ OCF₃ 4-F A-337 OC(O)CH₂C₆H₅ OCF₃ 4-F A-338 OC(O)CH₂Cl OCF₃ 4-F A-339 OC(O)CF₃ OCF₃ 4-F A-340 OC(O)CH₂OCH₃ OCF₃ 4-F A-341 OC(O)N(CH₃)₂ OCF₃ 4-F A-342 OC(O)OCH₂CH₃ OCF₃ 4-F A-343 OH Cl 5-F A-344 OCH₃ Cl 5-F A-345 OC(O)CH₃ Cl 5-F A-346 OC(O)CH₂CH₃ Cl 5-F A-347 OC(O)CH(CH₃)₂ Cl 5-F A-348 OC(O)C(CH₃)₃ Cl 5-F A-349 OC(O)c-C₃H₅ Cl 5-F A-350 OC(O)C₆H₅ Cl 5-F A-351 OC(O)CH₂C₆H₅ Cl 5-F A-352 OC(O)CH₂Cl Cl 5-F A-353 OC(O)CF₃ Cl 5-F A-354 OC(O)CH₂OCH₃ Cl 5-F A-355 OC(O)N(CH₃)₂ Cl 5-F A-356 OC(O)OCH₂CH₃ Cl 5-F A-357 OH F 5-F A-358 OCH₃ F 5-F A-359 OC(O)CH₃ F 5-F A-360 OC(O)CH₂CH₃ F 5-F A-361 OC(O)CH(CH₃)₂ F 5-F A-362 OC(O)C(CH₃)₃ F 5-F A-363 OC(O)c-C₃H₅ F 5-F A-364 OC(O)C₆H₅ F 5-F A-365 OC(O)CH₂C₆H₅ F 5-F A-366 OC(O)CH₂Cl F 5-F A-367 OC(O)CF₃ F 5-F A-368 OC(O)CH₂OCH₃ F 5-F A-369 OC(O)N(CH₃)₂ F 5-F A-370 OC(O)OCH₂CH₃ F 5-F A-371 OH NO₂ 5-F A-372 OCH₃ NO₂ 5-F A-373 OC(O)CH₃ NO₂ 5-F A-374 OC(O)CH₂CH₃ NO₂ 5-F A-375 OC(O)CH(CH₃)₂ NO₂ 5-F A-376 OC(O)C(CH₃)₃ NO₂ 5-F A-377 OC(O)c-C₃H₅ NO₂ 5-F A-378 OC(O)C₆H₅ NO₂ 5-F A-379 OC(O)CH₂C₆H₅ NO₂ 5-F A-380 OC(O)CH₂Cl NO₂ 5-F A-381 OC(O)CF₃ NO₂ 5-F A-382 OC(O)CH₂OCH₃ NO₂ 5-F A-383 OC(O)N(CH₃)₂ NO₂ 5-F A-384 OC(O)OCH₂CH₃ NO₂ 5-F A-385 OH CH₃ 5-F A-386 OCH₃ CH₃ 5-F A-387 OC(O)CH₃ CH₃ 5-F A-388 OC(O)CH₂CH₃ CH₃ 5-F A-389 OC(O)CH(CH₃)₂ CH₃ 5-F A-390 OC(O)C(CH₃)₃ CH₃ 5-F A-391 OC(O)c-C₃H₅ CH₃ 5-F A-392 OC(O)C₆H₅ CH₃ 5-F A-393 OC(O)CH₂C₆H₅ CH₃ 5-F A-394 OC(O)CH₂Cl CH₃ 5-F A-395 OC(O)CF₃ CH₃ 5-F A-396 OC(O)CH₂OCH₃ CH₃ 5-F A-397 OC(O)N(CH₃)₂ CH₃ 5-F A-398 OC(O)OCH₂CH₃ CH₃ 5-F A-399 OH OCH₃ 5-F A-400 OCH₃ OCH₃ 5-F A-401 OC(O)CH₃ OCH₃ 5-F A-402 OC(O)CH₂CH₃ OCH₃ 5-F A-403 OC(O)CH(CH₃)₂ OCH₃ 5-F A-404 OC(O)C(CH₃)₃ OCH₃ 5-F A-405 OC(O)c-C₃H₅ OCH₃ 5-F A-406 OC(O)C₆H₅ OCH₃ 5-F A-407 OC(O)CH₂C₆H₅ OCH₃ 5-F A-408 OC(O)CH₂Cl OCH₃ 5-F A-409 OC(O)CF₃ OCH₃ 5-F A-410 OC(O)CH₂OCH₃ OCH₃ 5-F A-411 OC(O)N(CH₃)₂ OCH₃ 5-F A-412 OC(O)OCH₂CH₃ OCH₃ 5-F A-413 OH CHF₂ 5-F A-414 OCH₃ CHF₂ 5-F A-415 OC(O)CH₃ CHF₂ 5-F A-416 OC(O)CH₂CH₃ CHF₂ 5-F A-417 OC(O)CH(CH₃)₂ CHF₂ 5-F A-418 OC(O)C(CH₃)₃ CHF₂ 5-F A-419 OC(O)c-C₃H₅ CHF₂ 5-F A-420 OC(O)C₆H₅ CHF₂ 5-F A-421 OC(O)CH₂C₆H₅ CHF₂ 5-F A-422 OC(O)CH₂Cl CHF₂ 5-F A-423 OC(O)CF₃ CHF₂ 5-F A-424 OC(O)CH₂OCH₃ CHF₂ 5-F A-425 OC(O)N(CH₃)₂ CHF₂ 5-F A-426 OC(O)OCH₂CH₃ CHF₂ 5-F A-427 OH CF₃ 5-F A-428 OCH₃ CF₃ 5-F A-429 OC(O)CH₃ CF₃ 5-F A-430 OC(O)CH₂CH₃ CF₃ 5-F A-431 OC(O)CH(CH₃)₂ CF₃ 5-F A-432 OC(O)C(CH₃)₃ CF₃ 5-F A-433 OC(O)c-C₃H₅ CF₃ 5-F A-434 OC(O)C₆H₅ CF₃ 5-F A-435 OC(O)CH₂C₆H₅ CF₃ 5-F A-436 OC(O)CH₂Cl CF₃ 5-F A-437 OC(O)CF₃ CF₃ 5-F A-438 OC(O)CH₂OCH₃ CF₃ 5-F A-439 OC(O)N(CH₃)₂ CF₃ 5-F A-440 OC(O)OCH₂CH₃ CF₃ 5-F A-441 OH OCHF₂ 5-F A-442 OCH₃ OCHF₂ 5-F A-443 OC(O)CH₃ OCHF₂ 5-F A-444 OC(O)CH₂CH₃ OCHF₂ 5-F A-445 OC(O)CH(CH₃)₂ OCHF₂ 5-F A-446 OC(O)C(CH₃)₃ OCHF₂ 5-F A-447 OC(O)c-C₃H₅ OCHF₂ 5-F A-448 OC(O)C₆H₅ OCHF₂ 5-F A-449 OC(O)CH₂C₆H₅ OCHF₂ 5-F A-450 OC(O)CH₂Cl OCHF₂ 5-F A-451 OC(O)CF₃ OCHF₂ 5-F A-452 OC(O)CH₂OCH₃ OCHF₂ 5-F A-453 OC(O)N(CH₃)₂ OCHF₂ 5-F A-454 OC(O)OCH₂CH₃ OCHF₂ 5-F A-455 OH OCF₃ 5-F A-456 OCH₃ OCF₃ 5-F A-457 OC(O)CH₃ OCF₃ 5-F A-458 OC(O)CH₂CH₃ OCF₃ 5-F A-459 OC(O)CH(CH₃)₂ OCF₃ 5-F A-460 OC(O)C(CH₃)₃ OCF₃ 5-F A-461 OC(O)c-C₃H₅ OCF₃ 5-F A-462 OC(O)C₆H₅ OCF₃ 5-F A-463 OC(O)CH₂C₆H₅ OCF₃ 5-F A-464 OC(O)CH₂Cl OCF₃ 5-F A-465 OC(O)CF₃ OCF₃ 5-F A-466 OC(O)CH₂OCH₃ OCF₃ 5-F A-467 OC(O)N(CH₃)₂ OCF₃ 5-F A-468 OC(O)OCH₂CH₃ OCF₃ 5-F A-469 OH Cl 6-F A-470 OCH₃ Cl 6-F A-471 OC(O)CH₃ Cl 6-F A-472 OC(O)CH₂CH₃ Cl 6-F A-473 OC(O)CH(CH₃)₂ Cl 6-F A-474 OC(O)C(CH₃)₃ Cl 6-F A-475 OC(O)c-C₃H₅ Cl 6-F A-476 OC(O)C₆H₅ Cl 6-F A-477 OC(O)CH₂C₆H₅ Cl 6-F A-478 OC(O)CH₂Cl Cl 6-F A-479 OC(O)CF₃ Cl 6-F A-480 OC(O)CH₂OCH₃ Cl 6-F A-481 OC(O)N(CH₃)₂ Cl 6-F A-482 OC(O)OCH₂CH₃ Cl 6-F A-483 OH F 6-F A-484 OCH₃ F 6-F A-485 OC(O)CH₃ F 6-F A-486 OC(O)CH₂CH₃ F 6-F A-487 OC(O)CH(CH₃)₂ F 6-F A-488 OC(O)C(CH₃)₃ F 6-F A-489 OC(O)c-C₃H₅ F 6-F A-490 OC(O)C₆H₅ F 6-F A-491 OC(O)CH₂C₆H₅ F 6-F A-492 OC(O)CH₂Cl F 6-F A-493 OC(O)CF₃ F 6-F A-494 OC(O)CH₂OCH₃ F 6-F A-495 OC(O)N(CH₃)₂ F 6-F A-496 OC(O)OCH₂CH₃ F 6-F A-497 OH NO₂ 6-F A-498 OCH₃ NO₂ 6-F A-499 OC(O)CH₃ NO₂ 6-F A-500 OC(O)CH₂CH₃ NO₂ 6-F A-501 OC(O)CH(CH₃)₂ NO₂ 6-F A-502 OC(O)C(CH₃)₃ NO₂ 6-F A-503 OC(O)c-C₃H₅ NO₂ 6-F A-504 OC(O)C₆H₅ NO₂ 6-F A-505 OC(O)CH₂C₆H₅ NO₂ 6-F A-506 OC(O)CH₂Cl NO₂ 6-F A-507 OC(O)CF₃ NO₂ 6-F A-508 OC(O)CH₂OCH₃ NO₂ 6-F A-509 OC(O)N(CH₃)₂ NO₂ 6-F A-510 OC(O)OCH₂CH₃ NO₂ 6-F A-511 OH CH₃ 6-F A-512 OCH₃ CH₃ 6-F A-513 OC(O)CH₃ CH₃ 6-F A-514 OC(O)CH₂CH₃ CH₃ 6-F A-515 OC(O)CH(CH₃)₂ CH₃ 6-F A-516 OC(O)C(CH₃)₃ CH₃ 6-F A-517 OC(O)c-C₃H₅ CH₃ 6-F A-518 OC(O)C₆H₅ CH₃ 6-F A-519 OC(O)CH₂C₆H₅ CH₃ 6-F A-520 OC(O)CH₂Cl CH₃ 6-F A-521 OC(O)CF₃ CH₃ 6-F A-522 OC(O)CH₂OCH₃ CH₃ 6-F A-523 OC(O)N(CH₃)₂ CH₃ 6-F A-524 OC(O)OCH₂CH₃ CH₃ 6-F A-525 OH OCH₃ 6-F A-526 OCH₃ OCH₃ 6-F A-527 OC(O)CH₃ OCH₃ 6-F A-528 OC(O)CH₂CH₃ OCH₃ 6-F A-529 OC(O)CH(CH₃)₂ OCH₃ 6-F A-530 OC(O)C(CH₃)₃ OCH₃ 6-F A-531 OC(O)c-C₃H₅ OCH₃ 6-F A-532 OC(O)C₆H₅ OCH₃ 6-F A-533 OC(O)CH₂C₆H₅ OCH₃ 6-F A-534 OC(O)CH₂Cl OCH₃ 6-F A-535 OC(O)CF₃ OCH₃ 6-F A-536 OC(O)CH₂OCH₃ OCH₃ 6-F A-537 OC(O)N(CH₃)₂ OCH₃ 6-F A-538 OC(O)OCH₂CH₃ OCH₃ 6-F A-539 OH CHF₂ 6-F A-540 OCH₃ CHF₂ 6-F A-541 OC(O)CH₃ CHF₂ 6-F A-542 OC(O)CH₂CH₃ CHF₂ 6-F A-543 OC(O)CH(CH₃)₂ CHF₂ 6-F A-544 OC(O)C(CH₃)₃ CHF₂ 6-F A-545 OC(O)c-C₃H₅ CHF₂ 6-F A-546 OC(O)C₆H₅ CHF₂ 6-F A-547 OC(O)CH₂C₆H₅ CHF₂ 6-F A-548 OC(O)CH₂Cl CHF₂ 6-F A-549 OC(O)CF₃ CHF₂ 6-F A-550 OC(O)CH₂OCH₃ CHF₂ 6-F A-551 OC(O)N(CH₃)₂ CHF₂ 6-F A-552 OC(O)OCH₂CH₃ CHF₂ 6-F A-553 OH CF₃ 6-F A-554 OCH₃ CF₃ 6-F A-555 OC(O)CH₃ CF₃ 6-F A-556 OC(O)CH₂CH₃ CF₃ 6-F A-557 OC(O)CH(CH₃)₂ CF₃ 6-F A-558 OC(O)C(CH₃)₃ CF₃ 6-F A-559 OC(O)c-C₃H₅ CF₃ 6-F A-560 OC(O)C₆H₅ CF₃ 6-F A-561 OC(O)CH₂C₆H₅ CF₃ 6-F A-562 OC(O)CH₂Cl CF₃ 6-F A-563 OC(O)CF₃ CF₃ 6-F A-564 OC(O)CH₂OCH₃ CF₃ 6-F A-565 OC(O)N(CH₃)₂ CF₃ 6-F A-566 OC(O)OCH₂CH₃ CF₃ 6-F A-567 OH OCHF₂ 6-F A-568 OCH₃ OCHF₂ 6-F A-569 OC(O)CH₃ OCHF₂ 6-F A-570 OC(O)CH₂CH₃ OCHF₂ 6-F A-571 OC(O)CH(CH₃)₂ OCHF₂ 6-F A-572 OC(O)C(CH₃)₃ OCHF₂ 6-F A-573 OC(O)c-C₃H₅ OCHF₂ 6-F A-574 OC(O)C₆H₅ OCHF₂ 6-F A-575 OC(O)CH₂C₆H₅ OCHF₂ 6-F A-576 OC(O)CH₂Cl OCHF₂ 6-F A-577 OC(O)CF₃ OCHF₂ 6-F A-578 OC(O)CH₂OCH₃ OCHF₂ 6-F A-579 OC(O)N(CH₃)₂ OCHF₂ 6-F A-580 OC(O)OCH₂CH₃ OCHF₂ 6-F A-581 OH OCF₃ 6-F A-582 OCH₃ OCF₃ 6-F A-583 OC(O)CH₃ OCF₃ 6-F A-584 OC(O)CH₂CH₃ OCF₃ 6-F A-585 OC(O)CH(CH₃)₂ OCF₃ 6-F A-586 OC(O)C(CH₃)₃ OCF₃ 6-F A-587 OC(O)c-C₃H₅ OCF₃ 6-F A-588 OC(O)C₆H₅ OCF₃ 6-F A-589 OC(O)CH₂C₆H₅ OCF₃ 6-F A-590 OC(O)CH₂Cl OCF₃ 6-F A-591 OC(O)CF₃ OCF₃ 6-F A-592 OC(O)CH₂OCH₃ OCF₃ 6-F A-593 OC(O)N(CH₃)₂ OCF₃ 6-F A-594 OC(O)OCH₂CH₃ OCF₃ 6-F A-595 OH Cl 4-CF₃ A-596 OCH₃ Cl 4-CF₃ A-597 OC(O)CH₃ Cl 4-CF₃ A-598 OC(O)CH₂CH₃ Cl 4-CF₃ A-599 OC(O)CH(CH₃)₂ Cl 4-CF₃ A-600 OC(O)C(CH₃)₃ Cl 4-CF₃ A-601 OC(O)c-C₃H₅ Cl 4-CF₃ A-602 OC(O)C₆H₅ Cl 4-CF₃ A-603 OC(O)CH₂C₆H₅ Cl 4-CF₃ A-604 OC(O)CH₂Cl Cl 4-CF₃ A-605 OC(O)CF₃ Cl 4-CF₃ A-606 OC(O)CH₂OCH₃ Cl 4-CF₃ A-607 OC(O)N(CH₃)₂ Cl 4-CF₃ A-608 OC(O)OCH₂CH₃ Cl 4-CF₃ A-609 OH F 4-CF₃ A-610 OCH₃ F 4-CF₃ A-611 OC(O)CH₃ F 4-CF₃ A-612 OC(O)CH₂CH₃ F 4-CF₃ A-613 OC(O)CH(CH₃)₂ F 4-CF₃ A-614 OC(O)C(CH₃)₃ F 4-CF₃ A-615 OC(O)c-C₃H₅ F 4-CF₃ A-616 OC(O)C₆H₅ F 4-CF₃ A-617 OC(O)CH₂C₆H₅ F 4-CF₃ A-618 OC(O)CH₂Cl F 4-CF₃ A-619 OC(O)CF₃ F 4-CF₃ A-620 OC(O)CH₂OCH₃ F 4-CF₃ A-621 OC(O)N(CH₃)₂ F 4-CF₃ A-622 OC(O)OCH₂CH₃ F 4-CF₃ A-623 OH NO₂ 4-CF₃ A-624 OCH₃ NO₂ 4-CF₃ A-625 OC(O)CH₃ NO₂ 4-CF₃ A-626 OC(O)CH₂CH₃ NO₂ 4-CF₃ A-627 OC(O)CH(CH₃)₂ NO₂ 4-CF₃ A-628 OC(O)C(CH₃)₃ NO₂ 4-CF₃ A-629 OC(O)c-C₃H₅ NO₂ 4-CF₃ A-630 OC(O)C₆H₅ NO₂ 4-CF₃ A-631 OC(O)CH₂C₆H₅ NO₂ 4-CF₃ A-632 OC(O)CH₂Cl NO₂ 4-CF₃ A-633 OC(O)CF₃ NO₂ 4-CF₃ A-634 OC(O)CH₂OCH₃ NO₂ 4-CF₃ A-635 OC(O)N(CH₃)₂ NO₂ 4-CF₃ A-636 OC(O)OCH₂CH₃ NO₂ 4-CF₃ A-637 OH CH₃ 4-CF₃ A-638 OCH₃ CH₃ 4-CF₃ A-639 OC(O)CH₃ CH₃ 4-CF₃ A-640 OC(O)CH₂CH₃ CH₃ 4-CF₃ A-641 OC(O)CH(CH₃)₂ CH₃ 4-CF₃ A-642 OC(O)C(CH₃)₃ CH₃ 4-CF₃ A-643 OC(O)c-C₃H₅ CH₃ 4-CF₃ A-644 OC(O)C₆H₅ CH₃ 4-CF₃ A-645 OC(O)CH₂C₆H₅ CH₃ 4-CF₃ A-646 OC(O)CH₂Cl CH₃ 4-CF₃ A-647 OC(O)CF₃ CH₃ 4-CF₃ A-648 OC(O)CH₂OCH₃ CH₃ 4-CF₃ A-649 OC(O)N(CH₃)₂ CH₃ 4-CF₃ A-650 OC(O)OCH₂CH₃ CH₃ 4-CF₃ A-651 OH OCH₃ 4-CF₃ A-652 OCH₃ OCH₃ 4-CF₃ A-653 OC(O)CH₃ OCH₃ 4-CF₃ A-654 OC(O)CH₂CH₃ OCH₃ 4-CF₃ A-655 OC(O)CH(CH₃)₂ OCH₃ 4-CF₃ A-656 OC(O)C(CH₃)₃ OCH₃ 4-CF₃ A-657 OC(O)c-C₃H₅ OCH₃ 4-CF₃ A-658 OC(O)C₆H₅ OCH₃ 4-CF₃ A-659 OC(O)CH₂C₆H₅ OCH₃ 4-CF₃ A-660 OC(O)CH₂Cl OCH₃ 4-CF₃ A-661 OC(O)CF₃ OCH₃ 4-CF₃ A-662 OC(O)CH₂OCH₃ OCH₃ 4-CF₃ A-663 OC(O)N(CH₃)₂ OCH₃ 4-CF₃ A-664 OC(O)OCH₂CH₃ OCH₃ 4-CF₃ A-665 OH CHF₂ 4-CF₃ A-666 OCH₃ CHF₂ 4-CF₃ A-667 OC(O)CH₃ CHF₂ 4-CF₃ A-668 OC(O)CH₂CH₃ CHF₂ 4-CF₃ A-669 OC(O)CH(CH₃)₂ CHF₂ 4-CF₃ A-670 OC(O)C(CH₃)₃ CHF₂ 4-CF₃ A-671 OC(O)c-C₃H₅ CHF₂ 4-CF₃ A-672 OC(O)C₆H₅ CHF₂ 4-CF₃ A-673 OC(O)CH₂C₆H₅ CHF₂ 4-CF₃ A-674 OC(O)CH₂Cl CHF₂ 4-CF₃ A-675 OC(O)CF₃ CHF₂ 4-CF₃ A-676 OC(O)CH₂OCH₃ CHF₂ 4-CF₃ A-677 OC(O)N(CH₃)₂ CHF₂ 4-CF₃ A-678 OC(O)OCH₂CH₃ CHF₂ 4-CF₃ A-679 OH CF₃ 4-CF₃ A-680 OCH₃ CF₃ 4-CF₃ A-681 OC(O)CH₃ CF₃ 4-CF₃ A-682 OC(O)CH₂CH₃ CF₃ 4-CF₃ A-683 OC(O)CH(CH₃)₂ CF₃ 4-CF₃ A-684 OC(O)C(CH₃)₃ CF₃ 4-CF₃ A-685 OC(O)c-C₃H₅ CF₃ 4-CF₃ A-686 OC(O)C₆H₅ CF₃ 4-CF₃ A-687 OC(O)CH₂C₆H₅ CF₃ 4-CF₃ A-688 OC(O)CH₂Cl CF₃ 4-CF₃ A-689 OC(O)CF₃ CF₃ 4-CF₃ A-690 OC(O)CH₂OCH₃ CF₃ 4-CF₃ A-691 OC(O)N(CH₃)₂ CF₃ 4-CF₃ A-692 OC(O)OCH₂CH₃ CF₃ 4-CF₃ A-693 OH OCHF₂ 4-CF₃ A-694 OCH₃ OCHF₂ 4-CF₃ A-695 OC(O)CH₃ OCHF₂ 4-CF₃ A-696 OC(O)CH₂CH₃ OCHF₂ 4-CF₃ A-697 OC(O)CH(CH₃)₂ OCHF₂ 4-CF₃ A-698 OC(O)C(CH₃)₃ OCHF₂ 4-CF₃ A-699 OC(O)c-C₃H₅ OCHF₂ 4-CF₃ A-700 OC(O)C₆H₅ OCHF₂ 4-CF₃ A-701 OC(O)CH₂C₆H₅ OCHF₂ 4-CF₃ A-702 OC(O)CH₂Cl OCHF₂ 4-CF₃ A-703 OC(O)CF₃ OCHF₂ 4-CF₃ A-704 OC(O)CH₂OCH₃ OCHF₂ 4-CF₃ A-705 OC(O)N(CH₃)₂ OCHF₂ 4-CF₃ A-706 OC(O)OCH₂CH₃ OCHF₂ 4-CF₃ A-707 OH OCF₃ 4-CF₃ A-708 OCH₃ OCF₃ 4-CF₃ A-709 OC(O)CH₃ OCF₃ 4-CF₃ A-710 OC(O)CH₂CH₃ OCF₃ 4-CF₃ A-711 OC(O)CH(CH₃)₂ OCF₃ 4-CF₃ A-712 OC(O)C(CH₃)₃ OCF₃ 4-CF₃ A-713 OC(O)c-C₃H₅ OCF₃ 4-CF₃ A-714 OC(O)C₆H₅ OCF₃ 4-CF₃ A-715 OC(O)CH₂C₆H₅ OCF₃ 4-CF₃ A-716 OC(O)CH₂Cl OCF₃ 4-CF₃ A-717 OC(O)CF₃ OCF₃ 4-CF₃ A-718 OC(O)CH₂OCH₃ OCF₃ 4-CF₃ A-719 OC(O)N(CH₃)₂ OCF₃ 4-CF₃ A-720 OC(O)OCH₂CH₃ OCF₃ 4-CF₃ A-721 OH Cl 5-CF₃ A-722 OCH₃ Cl 5-CF₃ A-723 OC(O)CH₃ Cl 5-CF₃ A-724 OC(O)CH₂CH₃ Cl 5-CF₃ A-725 OC(O)CH(CH₃)₂ Cl 5-CF₃ A-726 OC(O)C(CH₃)₃ Cl 5-CF₃ A-727 OC(O)c-C₃H₅ Cl 5-CF₃ A-728 OC(O)C₆H₅ Cl 5-CF₃ A-729 OC(O)CH₂C₆H₅ Cl 5-CF₃ A-730 OC(O)CH₂Cl Cl 5-CF₃ A-731 OC(O)CF₃ Cl 5-CF₃ A-732 OC(O)CH₂OCH₃ Cl 5-CF₃ A-733 OC(O)N(CH₃)₂ Cl 5-CF₃ A-734 OC(O)OCH₂CH₃ Cl 5-CF₃ A-735 OH F 5-CF₃ A-736 OCH₃ F 5-CF₃ A-737 OC(O)CH₃ F 5-CF₃ A-738 OC(O)CH₂CH₃ F 5-CF₃ A-739 OC(O)CH(CH₃)₂ F 5-CF₃ A-740 OC(O)C(CH₃)₃ F 5-CF₃ A-741 OC(O)c-C₃H₅ F 5-CF₃ A-742 OC(O)C₆H₅ F 5-CF₃ A-743 OC(O)CH₂C₆H₅ F 5-CF₃ A-744 OC(O)CH₂Cl F 5-CF₃ A-745 OC(O)CF₃ F 5-CF₃ A-746 OC(O)CH₂OCH₃ F 5-CF₃ A-747 OC(O)N(CH₃)₂ F 5-CF₃ A-748 OC(O)OCH₂CH₃ F 5-CF₃ A-749 OH NO₂ 5-CF₃ A-750 OCH₃ NO₂ 5-CF₃ A-751 OC(O)CH₃ NO₂ 5-CF₃ A-752 OC(O)CH₂CH₃ NO₂ 5-CF₃ A-753 OC(O)CH(CH₃)₂ NO₂ 5-CF₃ A-754 OC(O)C(CH₃)₃ NO₂ 5-CF₃ A-755 OC(O)c-C₃H₅ NO₂ 5-CF₃ A-756 OC(O)C₆H₅ NO₂ 5-CF₃ A-757 OC(O)CH₂C₆H₅ NO₂ 5-CF₃ A-758 OC(O)CH₂Cl NO₂ 5-CF₃ A-759 OC(O)CF₃ NO₂ 5-CF₃ A-760 OC(O)CH₂OCH₃ NO₂ 5-CF₃ A-761 OC(O)N(CH₃)₂ NO₂ 5-CF₃ A-762 OC(O)OCH₂CH₃ NO₂ 5-CF₃ A-763 OH CH₃ 5-CF₃ A-764 OCH₃ CH₃ 5-CF₃ A-765 OC(O)CH₃ CH₃ 5-CF₃ A-766 OC(O)CH₂CH₃ CH₃ 5-CF₃ A-767 OC(O)CH(CH₃)₂ CH₃ 5-CF₃ A-768 OC(O)C(CH₃)₃ CH₃ 5-CF₃ A-769 OC(O)c-C₃H₅ CH₃ 5-CF₃ A-770 OC(O)C₆H₅ CH₃ 5-CF₃ A-771 OC(O)CH₂C₆H₅ CH₃ 5-CF₃ A-772 OC(O)CH₂Cl CH₃ 5-CF₃ A-773 OC(O)CF₃ CH₃ 5-CF₃ A-774 OC(O)CH₂OCH₃ CH₃ 5-CF₃ A-775 OC(O)N(CH₃)₂ CH₃ 5-CF₃ A-776 OC(O)OCH₂CH₃ CH₃ 5-CF₃ A-777 OH OCH₃ 5-CF₃ A-778 OCH₃ OCH₃ 5-CF₃ A-779 OC(O)CH₃ OCH₃ 5-CF₃ A-780 OC(O)CH₂CH₃ OCH₃ 5-CF₃ A-781 OC(O)CH(CH₃)₂ OCH₃ 5-CF₃ A-782 OC(O)C(CH₃)₃ OCH₃ 5-CF₃ A-783 OC(O)c-C₃H₅ OCH₃ 5-CF₃ A-784 OC(O)C₆H₅ OCH₃ 5-CF₃ A-785 OC(O)CH₂C₆H₅ OCH₃ 5-CF₃ A-786 OC(O)CH₂Cl OCH₃ 5-CF₃ A-787 OC(O)CF₃ OCH₃ 5-CF₃ A-788 OC(O)CH₂OCH₃ OCH₃ 5-CF₃ A-789 OC(O)N(CH₃)₂ OCH₃ 5-CF₃ A-790 OC(O)OCH₂CH₃ OCH₃ 5-CF₃ A-791 OH CHF₂ 5-CF₃ A-792 OCH₃ CHF₂ 5-CF₃ A-793 OC(O)CH₃ CHF₂ 5-CF₃ A-794 OC(O)CH₂CH₃ CHF₂ 5-CF₃ A-795 OC(O)CH(CH₃)₂ CHF₂ 5-CF₃ A-796 OC(O)C(CH₃)₃ CHF₂ 5-CF₃ A-797 OC(O)c-C₃H₅ CHF₂ 5-CF₃ A-798 OC(O)C₆H₅ CHF₂ 5-CF₃ A-799 OC(O)CH₂C₆H₅ CHF₂ 5-CF₃ A-800 OC(O)CH₂Cl CHF₂ 5-CF₃ A-801 OC(O)CF₃ CHF₂ 5-CF₃ A-802 OC(O)CH₂OCH₃ CHF₂ 5-CF₃ A-803 OC(O)N(CH₃)₂ CHF₂ 5-CF₃ A-804 OC(O)OCH₂CH₃ CHF₂ 5-CF₃ A-805 OH CF₃ 5-CF₃ A-806 OCH₃ CF₃ 5-CF₃ A-807 OC(O)CH₃ CF₃ 5-CF₃ A-808 OC(O)CH₂CH₃ CF₃ 5-CF₃ A-809 OC(O)CH(CH₃)₂ CF₃ 5-CF₃ A-810 OC(O)C(CH₃)₃ CF₃ 5-CF₃ A-811 OC(O)c-C₃H₅ CF₃ 5-CF₃ A-812 OC(O)C₆H₅ CF₃ 5-CF₃ A-813 OC(O)CH₂C₆H₅ CF₃ 5-CF₃ A-814 OC(O)CH₂Cl CF₃ 5-CF₃ A-815 OC(O)CF₃ CF₃ 5-CF₃ A-816 OC(O)CH₂OCH₃ CF₃ 5-CF₃ A-817 OC(O)N(CH₃)₂ CF₃ 5-CF₃ A-818 OC(O)OCH₂CH₃ CF₃ 5-CF₃ A-819 OH OCHF₂ 5-CF₃ A-820 OCH₃ OCHF₂ 5-CF₃ A-821 OC(O)CH₃ OCHF₂ 5-CF₃ A-822 OC(O)CH₂CH₃ OCHF₂ 5-CF₃ A-823 OC(O)CH(CH₃)₂ OCHF₂ 5-CF₃ A-824 OC(O)C(CH₃)₃ OCHF₂ 5-CF₃ A-825 OC(O)c-C₃H₅ OCHF₂ 5-CF₃ A-826 OC(O)C₆H₅ OCHF₂ 5-CF₃ A-827 OC(O)CH₂C₆H₅ OCHF₂ 5-CF₃ A-828 OC(O)CH₂Cl OCHF₂ 5-CF₃ A-829 OC(O)CF₃ OCHF₂ 5-CF₃ A-830 OC(O)CH₂OCH₃ OCHF₂ 5-CF₃ A-831 OC(O)N(CH₃)₂ OCHF₂ 5-CF₃ A-832 OC(O)OCH₂CH₃ OCHF₂ 5-CF₃ A-833 OH OCF₃ 5-CF₃ A-834 OCH₃ OCF₃ 5-CF₃ A-835 OC(O)CH₃ OCF₃ 5-CF₃ A-836 OC(O)CH₂CH₃ OCF₃ 5-CF₃ A-837 OC(O)CH(CH₃)₂ OCF₃ 5-CF₃ A-838 OC(O)C(CH₃)₃ OCF₃ 5-CF₃ A-839 OC(O)c-C₃H₅ OCF₃ 5-CF₃ A-840 OC(O)C₆H₅ OCF₃ 5-CF₃ A-841 OC(O)CH₂C₆H₅ OCF₃ 5-CF₃ A-842 OC(O)CH₂Cl OCF₃ 5-CF₃ A-843 OC(O)CF₃ OCF₃ 5-CF₃ A-844 OC(O)CH₂OCH₃ OCF₃ 5-CF₃ A-845 OC(O)N(CH₃)₂ OCF₃ 5-CF₃ A-846 OC(O)OCH₂CH₃ OCF₃ 5-CF₃ A-847 OH Cl 3,6-F₂ A-848 OCH₃ Cl 3,6-F₂ A-849 OC(O)CH₃ Cl 3,6-F₂ A-850 OC(O)CH₂CH₃ Cl 3,6-F₂ A-851 OC(O)CH(CH₃)₂ Cl 3,6-F₂ A-852 OC(O)C(CH₃)₃ Cl 3,6-F₂ A-853 OC(O)c-C₃H₅ Cl 3,6-F₂ A-854 OC(O)C₆H₅ Cl 3,6-F₂ A-855 OC(O)CH₂C₆H₅ Cl 3,6-F₂ A-856 OC(O)CH₂Cl Cl 3,6-F₂ A-857 OC(O)CF₃ Cl 3,6-F₂ A-858 OC(O)CH₂OCH₃ Cl 3,6-F₂ A-859 OC(O)N(CH₃)₂ Cl 3,6-F₂ A-860 OC(O)OCH₂CH₃ Cl 3,6-F₂ A-861 OH F 3,6-F₂ A-862 OCH₃ F 3,6-F₂ A-863 OC(O)CH₃ F 3,6-F₂ A-864 OC(O)CH₂CH₃ F 3,6-F₂ A-865 OC(O)CH(CH₃)₂ F 3,6-F₂ A-866 OC(O)C(CH₃)₃ F 3,6-F₂ A-867 OC(O)c-C₃H₅ F 3,6-F₂ A-868 OC(O)C₆H₅ F 3,6-F₂ A-869 OC(O)CH₂C₆H₅ F 3,6-F₂ A-870 OC(O)CH₂Cl F 3,6-F₂ A-871 OC(O)CF₃ F 3,6-F₂ A-872 OC(O)CH₂OCH₃ F 3,6-F₂ A-873 OC(O)N(CH₃)₂ F 3,6-F₂ A-874 OC(O)OCH₂CH₃ F 3,6-F₂ A-875 OH NO₂ 3,6-F₂ A-876 OCH₃ NO₂ 3,6-F₂ A-877 OC(O)CH₃ NO₂ 3,6-F₂ A-878 OC(O)CH₂CH₃ NO₂ 3,6-F₂ A-879 OC(O)CH(CH₃)₂ NO₂ 3,6-F₂ A-880 OC(O)C(CH₃)₃ NO₂ 3,6-F₂ A-881 OC(O)c-C₃H₅ NO₂ 3,6-F₂ A-882 OC(O)C₆H₅ NO₂ 3,6-F₂ A-883 OC(O)CH₂C₆H₅ NO₂ 3,6-F₂ A-884 OC(O)CH₂Cl NO₂ 3,6-F₂ A-885 OC(O)CF₃ NO₂ 3,6-F₂ A-886 OC(O)CH₂OCH₃ NO₂ 3,6-F₂ A-887 OC(O)N(CH₃)₂ NO₂ 3,6-F₂ A-888 OC(O)OCH₂CH₃ NO₂ 3,6-F₂ A-889 OH CH₃ 3,6-F₂ A-890 OCH₃ CH₃ 3,6-F₂ A-891 OC(O)CH₃ CH₃ 3,6-F₂ A-892 OC(O)CH₂CH₃ CH₃ 3,6-F₂ A-893 OC(O)CH(CH₃)₂ CH₃ 3,6-F₂ A-894 OC(O)C(CH₃)₃ CH₃ 3,6-F₂ A-895 OC(O)c-C₃H₅ CH₃ 3,6-F₂ A-896 OC(O)C₆H₅ CH₃ 3,6-F₂ A-897 OC(O)CH₂C₆H₅ CH₃ 3,6-F₂ A-898 OC(O)CH₂Cl CH₃ 3,6-F₂ A-899 OC(O)CF₃ CH₃ 3,6-F₂ A-900 OC(O)CH₂OCH₃ CH₃ 3,6-F₂ A-901 OC(O)N(CH₃)₂ CH₃ 3,6-F₂ A-902 OC(O)OCH₂CH₃ CH₃ 3,6-F₂ A-903 OH OCH₃ 3,6-F₂ A-904 OCH₃ OCH₃ 3,6-F₂ A-905 OC(O)CH₃ OCH₃ 3,6-F₂ A-906 OC(O)CH₂CH₃ OCH₃ 3,6-F₂ A-907 OC(O)CH(CH₃)₂ OCH₃ 3,6-F₂ A-908 OC(O)C(CH₃)₃ OCH₃ 3,6-F₂ A-909 OC(O)c-C₃H₅ OCH₃ 3,6-F₂ A-910 OC(O)C₆H₅ OCH₃ 3,6-F₂ A-911 OC(O)CH₂C₆H₅ OCH₃ 3,6-F₂ A-912 OC(O)CH₂Cl OCH₃ 3,6-F₂ A-913 OC(O)CF₃ OCH₃ 3,6-F₂ A-914 OC(O)CH₂OCH₃ OCH₃ 3,6-F₂ A-915 OC(O)N(CH₃)₂ OCH₃ 3,6-F₂ A-916 OC(O)OCH₂CH₃ OCH₃ 3,6-F₂ A-917 OH CHF₂ 3,6-F₂ A-918 OCH₃ CHF₂ 3,6-F₂ A-919 OC(O)CH₃ CHF₂ 3,6-F₂ A-920 OC(O)CH₂CH₃ CHF₂ 3,6-F₂ A-921 OC(O)CH(CH₃)₂ CHF₂ 3,6-F₂ A-922 OC(O)C(CH₃)₃ CHF₂ 3,6-F₂ A-923 OC(O)c-C₃H₅ CHF₂ 3,6-F₂ A-924 OC(O)C₆H₅ CHF₂ 3,6-F₂ A-925 OC(O)CH₂C₆H₅ CHF₂ 3,6-F₂ A-926 OC(O)CH₂Cl CHF₂ 3,6-F₂ A-927 OC(O)CF₃ CHF₂ 3,6-F₂ A-928 OC(O)CH₂OCH₃ CHF₂ 3,6-F₂ A-929 OC(O)N(CH₃)₂ CHF₂ 3,6-F₂ A-930 OC(O)OCH₂CH₃ CHF₂ 3,6-F₂ A-931 OH CF₃ 3,6-F₂ A-932 OCH₃ CF₃ 3,6-F₂ A-933 OC(O)CH₃ CF₃ 3,6-F₂ A-934 OC(O)CH₂CH₃ CF₃ 3,6-F₂ A-935 OC(O)CH(CH₃)₂ CF₃ 3,6-F₂ A-936 OC(O)C(CH₃)₃ CF₃ 3,6-F₂ A-937 OC(O)c-C₃H₅ CF₃ 3,6-F₂ A-938 OC(O)C₆H₅ CF₃ 3,6-F₂ A-939 OC(O)CH₂C₆H₅ CF₃ 3,6-F₂ A-940 OC(O)CH₂Cl CF₃ 3,6-F₂ A-941 OC(O)CF₃ CF₃ 3,6-F₂ A-942 OC(O)CH₂OCH₃ CF₃ 3,6-F₂ A-943 OC(O)N(CH₃)₂ CF₃ 3,6-F₂ A-944 OC(O)OCH₂CH₃ CF₃ 3,6-F₂ A-945 OH OCHF₂ 3,6-F₂ A-946 OCH₃ OCHF₂ 3,6-F₂ A-947 OC(O)CH₃ OCHF₂ 3,6-F₂ A-948 OC(O)CH₂CH₃ OCHF₂ 3,6-F₂ A-949 OC(O)CH(CH₃)₂ OCHF₂ 3,6-F₂ A-950 OC(O)C(CH₃)₃ OCHF₂ 3,6-F₂ A-951 OC(O)c-C₃H₅ OCHF₂ 3,6-F₂ A-952 OC(O)C₆H₅ OCHF₂ 3,6-F₂ A-953 OC(O)CH₂C₆H₅ OCHF₂ 3,6-F₂ A-954 OC(O)CH₂Cl OCHF₂ 3,6-F₂ A-955 OC(O)CF₃ OCHF₂ 3,6-F₂ A-956 OC(O)CH₂OCH₃ OCHF₂ 3,6-F₂ A-957 OC(O)N(CH₃)₂ OCHF₂ 3,6-F₂ A-958 OC(O)OCH₂CH₃ OCHF₂ 3,6-F₂ A-959 OH OCF₃ 3,6-F₂ A-960 OCH₃ OCF₃ 3,6-F₂ A-961 OC(O)CH₃ OCF₃ 3,6-F₂ A-962 OC(O)CH₂CH₃ OCF₃ 3,6-F₂ A-963 OC(O)CH(CH₃)₂ OCF₃ 3,6-F₂ A-964 OC(O)C(CH₃)₃ OCF₃ 3,6-F₂ A-965 OC(O)c-C₃H₅ OCF₃ 3,6-F₂ A-966 OC(O)C₆H₅ OCF₃ 3,6-F₂ A-967 OC(O)CH₂C₆H₅ OCF₃ 3,6-F₂ A-968 OC(O)CH₂Cl OCF₃ 3,6-F₂ A-969 OC(O)CF₃ OCF₃ 3,6-F₂ A-970 OC(O)CH₂OCH₃ OCF₃ 3,6-F₂ A-971 OC(O)N(CH₃)₂ OCF₃ 3,6-F₂ A-972 OC(O)OCH₂CH₃ OCF₃ 3,6-F₂

The compounds I and their agriculturally useful salts are suitable, both as isomer mixtures and in the form of the pure isomers, as herbicides. They are suitable as such or as an appropriately formulated composition. The herbicidal compositions comprising the compound I, in particular the preferred aspects thereof, control vegetation on non-crop areas very efficiently, especially at high rates of application. They act against broad-leaved weeds and weed grasses in crops such as wheat, rice, corn, soybeans and cotton without causing any significant damage to the crop plants. This effect is mainly observed at low rates of application.

Depending on the application method in question, the compounds I, in particular the preferred aspects thereof, or compositions comprising them can additionally be employed in a further number of crop plants for eliminating unwanted plants. Examples of suitable crops are the following:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Avena sativa, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Brassica oleracea, Brassica nigra, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pistacia vera, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Prunus armeniaca, Prunus cerasus, Prunus dulcis and Prunus domestica, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Sinapis alba, Solanum tuberosum, Sorghum bicolor (S. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticale, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.

The term “crop plants” also includes plants which have been modified by breeding, mutagenesis or genetic engineering. Genetically modified plants are plants whose genetic material has been modified in a manner which does not occur under natural conditions by crossing, mutations or natural recombination (i.e. reassembly of the genetic information). Here, in general, one or more genes are integrated into the genetic material of the plant to improve the properties of the plant.

Accordingly, the term “crop plants” also includes plants which, by breeding and genetic engineering, have acquired tolerance to certain classes of herbicides, such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, acetolactate synthase (ALS) inhibitors, such as, for example, sulfonylureas (EP-A 257 993, U.S. Pat. No. 5,013,659) or imidazolinones (see, for example, U.S. Pat. No. 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073), enolpyruvylshikimate 3-phosphate synthase (EPSPS) inhibitors, such as, for example, glyphosate (see, for example, WO 92/00377), glutamine synthetase (GS) inhibitors, such as, for example, glufosinate (see, for example, EP-A 242 236, EP-A 242 246), or oxynil herbicides (see, for example, U.S. Pat. No. 5,559,024).

Numerous crop plants, for example Clearfield® oilseed rape, tolerant to imidazolinones, for example imazamox, have been generated with the aid of classic breeding methods (mutagenesis). Crop plants such as soybeans, cotton, corn, beet and oilseed rape, resistant to glyphosate or glufosinate, which are available under the tradenames RoundupReady® (glyphosate) and Liberty Link® (glufosinate) have been generated with the aid of genetic engineering methods.

Accordingly, the term “crop plants” also includes plants which, with the aid of genetic engineering, produce one or more toxins, for example those of the bacterial strain Bacillus ssp. Toxins which are produced by such genetically modified plants include, for example, insecticidal proteins of Bacillus spp., in particular B. thuringiensis, such as the endotoxins Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, Cry9c, Cry34Ab1 or Cry35Ab1; or vegetative insecticidal proteins (VIPs), for example VIP1, VIP2, VIP3, or VIP3A; insecticidal proteins of nematode-colonizing bacteria, for example Photorhabdus spp. or Xenorhabdus spp.; toxins of animal organisms, for example wasp, spider or scorpion toxins; fungal toxins, for example from Streptomycetes; plant lectins, for example from peas or barley; agglutinins; proteinase inhibitors, for example trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors, ribosome-inactivating proteins (RIPs), for example ricin, corn-RIP, abrin, luffin, saporin or bryodin; steroid-metabolizing enzymes, for example 3-hydroxysteroid oxidase, ecdysteroid-IDP glycosyl transferase, cholesterol oxidase, ecdysone inhibitors, or HMG-CoA reductase; ion channel blockers, for example inhibitors of sodium channels or calcium channels; juvenile hormone esterase; receptors of the diuretic hormone (helicokinin receptors); stilbene synthase, bibenzyl synthase, chitinases and glucanases. In the plants, these toxins may also be produced as pretoxins, hybrid proteins or truncated or otherwise modified proteins. Hybrid proteins are characterized by a novel combination of different protein domains (see, for example, WO 2002/015701). Further examples of such toxins or genetically modified plants which produce these toxins are disclosed in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/018810 and WO 03/052073. The methods for producing these genetically modified plants are known to the person skilled in the art and disclosed, for example, in the publications mentioned above. Numerous of the toxins mentioned above bestow, upon the plants by which they are produced, tolerance to pests from all taxonomic classes of arthropods, in particular to beetles (Coeleropta), dipterans (Diptera) and butterflies (Lepidoptera) and to nematodes (Nematoda).

Genetically modified plants which produce one or more genes coding for insecticidal toxins are described, for example, in the publications mentioned above, and some of them are commercially available, such as, for example, YieldGard® (corn varieties producing the toxin Cry1Ab), YieldGard® Plus (corn varieties which produce the toxins Cry1Ab and Cry3Bb1), Starlink® (corn varieties which produce the toxin Cry9c), Herculex® RW (corn varieties which produce the toxins Cry34Ab1, Cry35Ab1 and the enzyme phosphinothricin-N-acetyltransferase [PAT]); NuCOTN® 33B (cotton varieties which produce the toxin Cry1Ac), Bollgard® I (cotton varieties which produce the toxin Cry1Ac), Bollgard® II (cotton varieties which produce the toxins Cry1Ac and Cry2Ab2); VIPCOT® (cotton varieties which produce a VIP toxin); NewLeaf® (potato varieties which produce the toxin Cry3A); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt11 (for example Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France (corn varieties which produce the toxin Cry1Ab and the PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn varieties which produce a modified version of the toxin Cry3A, see WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn varieties which produce the toxin Cry3Bb1), IPC 531 from Monsanto Europe S.A., Belgium (cotton varieties which produce a modified version of the toxin Cry1Ac) and 1507 from Pioneer Overseas Corporation, Belgium (corn varieties which produce the toxin Cry1F and the PAT enzyme).

Accordingly, the term “crop plants” also includes plants which, with the aid of genetic engineering, produce one or more proteins which are more robust or have increased resistance to bacterial, viral or fungal pathogens, such as, for example, pathogenesis-related proteins (PR proteins, see EP-A 392 225), resistance proteins (for example potato varieties producing two resistance genes against Phytophthora infestans from the wild Mexican potato Solanum bulbocastanum) or T4 lysozyme (for example potato cultivars which, by producing this protein, are resistant to bacteria such as Erwinia amylvora).

Accordingly, the term “crop plants” also includes plants whose productivity has been improved with the aid of genetic engineering methods, for example by enhancing the potential yield (for example biomass, grain yield, starch, oil or protein content), tolerance to drought, salt or other limiting environmental factors or resistance to pests and fungal, bacterial and viral pathogens.

The term “crop plants” also includes plants whose ingredients have been modified with the aid of genetic engineering methods in particular for improving human or animal diet, for example by oil plants producing health-promoting long-chain omega 3 fatty acids or monounsaturated omega 9 fatty acids (for example Nexera® oilseed rape).

The term “crop plants” also includes plants which have been modified with the aid of genetic engineering methods for improving the production of raw materials, for example by increasing the amylopectin content of potatoes (Amflora® potato).

Furthermore, it has been found that the compounds of the formula I are also suitable for the defoliation and/or desiccation of plant parts, for which crop plants such as cotton, potato, oilseed rape, sunflower, soybean or field beans, in particular cotton, are suitable. In this regard, there have been found compositions for the desiccation and/or defoliation of plants, processes for preparing these compositions and methods for desiccating and/or defoliating plants using the compounds of the formula I.

As desiccants, the compounds of the formula I are particularly suitable for desiccating the above-ground parts of crop plants such as potato, oilseed rape, sunflower and soybean, but also cereals. This makes possible the fully mechanical harvesting of these important crop plants.

Also of economic interest is to facilitate harvesting, which is made possible by concentrating within a certain period of time the dehiscence, or reduction of adhesion to the tree, in citrus fruit, olives and other species and varieties of pomaceous fruit, stone fruit and nuts. The same mechanism, i.e. the promotion of the development of abscission tissue between fruit part or leaf part and shoot part of the plants is also essential for the readily controllable defoliation of useful plants, in particular cotton.

Moreover, a shortening of the time interval in which the individual cotton plants mature leads to an increased fiber quality after harvesting.

The compounds I, or the herbicidal compositions comprising the compounds I, can be used, for example, in the form of ready-to-spray aqueous solutions, powders, suspensions, also highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for broadcasting, or granules, by means of spraying, atomizing, dusting, spreading, watering or treatment of the seed or mixing with the seed. The use forms depend on the intended purpose; in each case, they should ensure the finest possible distribution of the active ingredients according to the invention.

The herbicidal compositions comprise a herbicidally effective amount of at least one compound of the formula I or an agriculturally useful salt of I, and auxiliaries which are customary for the formulation of crop protection agents.

Examples of auxiliaries customary for the formulation of crop protection agents are inert auxiliaries, solid carriers, surfactants (such as dispersants, protective colloids, emulsifiers, wetting agents and tackifiers), organic and inorganic thickeners, bactericides, antifreeze agents, antifoams, optionally colorants and, for seed formulations, adhesives.

Examples of thickeners (i.e. compounds which impart to the formulation modified flow properties, i.e. high viscosity in the state of rest and low viscosity in motion) are polysaccharides, such as xanthan gum (Kelzan® from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum® (from R.T. Vanderbilt), and also organic and inorganic sheet minerals, such as Attaclay® (from Engelhardt).

Examples of antifoams are silicone emulsions (such as, for example, Silikon® SRE, Wacker or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof.

Bactericides can be added for stabilizing the aqueous herbicidal formulation. Examples of bactericides are bactericides based on dichlorophen and benzyl alcohol hemiformal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas), and also isothiazolinone derivates, such as alkylisothiazolinones and benzisothiazolinones (Acticide MBS from Thor Chemie).

Examples of antifreeze agents are ethylene glycol, propylene glycol, urea or glycerol.

Examples of colorants are both sparingly water-soluble pigments and water-soluble dyes. Examples which may be mentioned are the dyes known under the names Rhodamin B, C.I. Pigment Red 112 and C.I. Solvent Red 1, and also pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.

Examples of adhesives are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.

Suitable inert auxiliaries are, for example, the following:

mineral oil fractions of medium to high boiling point, such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, for example amines such as N-methylpyrrolidone, and water.

Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate and magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, or other solid carriers.

Suitable surfactants (adjuvants, wetting agents, tackifiers, dispersants and also emulsifiers) are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, for example lignosulfonic acids (e.g. Borrespers-types, Borregaard), phenolsulfonic acids, naphthalenesulfonic acids (Morwet types, Akzo Nobel) and dibutylnaphthalenesulfonic acid (Nekal types, BASF SE), and of fatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and also of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl or tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors and proteins, denatured proteins, polysaccharides (e.g. methylcellulose), hydrophobically modified starches, polyvinyl alcohol (Mowiol types Clariant), polycarboxylates (BASF SE, Sokalan types), polyalkoxylates, polyvinylamine (BASF SE, Lupamine types), polyethyleneimine (BASF SE, Lupasol types), polyvinylpyrrolidone and copolymers thereof.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active ingredients together with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers.

Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the compounds of the formula I or Ia, either as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetting agent, tackifier, dispersant or emulsifier. Alternatively, it is also possible to prepare concentrates comprising active substance, wetting agent, tackifier, dispersant or emulsifier and, if desired, solvent or oil, which are suitable for dilution with water.

The concentrations of the compounds of the formula I in the ready-to-use preparations can be varied within wide ranges. In general, the formulations comprise from 0.001 to 98% by weight, preferably 0.01 to 95% by weight of at least one active compound. The active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

The compounds I of the invention can for example be formulated as follows:

1. Products for Dilution with Water

A Water-Soluble Concentrates

10 parts by weight of active compound are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other adjuvants are added. The active compound dissolves upon dilution with water. This gives a formulation with an active compound content of 10% by weight.

B Dispersible Concentrates

20 parts by weight of active compound are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion. The active compound content is 20% by weight.

C Emulsifiable Concentrates

15 parts by weight of active compound are dissolved in 75 parts by weight of an organic solvent (e.g. alkylaromatics) with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion. The formulation has an active compound content of 15% by weight.

D Emulsions

25 parts by weight of active compound are dissolved in 35 parts by weight of an organic solvent (e.g. alkylaromatics) with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifier (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The formulation has an active compound content of 25% by weight.

E Suspensions

In an agitated ball mill, 20 parts by weight of active compound are comminuted with addition of 10 parts by weight of dispersants and wetters and 70 parts by weight of water or an organic solvent to give a fine active compound suspension. Dilution with water gives a stable suspension of the active compound. The active compound content in the formulation is 20% by weight.

F Water-Dispersible Granules and Water-Soluble Granules

50 parts by weight of active compound are ground finely with addition of 50 parts by weight of dispersants and wetters and made into water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound. The formulation has an active compound content of 50% by weight.

G Water-Dispersible Powders and Water-Soluble Powders

75 parts by weight of active compound are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound. The active compound content of the formulation is 75% by weight.

H Gel Formulations

In a ball mill, 20 parts by weight of active compound, 10 parts by weight of dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or of an organic solvent are ground to give a fine suspension. Dilution with water gives a stable suspension with active compound content of 20% by weight.

2. Products to be Applied Undiluted

I Dusts

5 parts by weight of active compound are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dusting powder with an active compound content of 5% by weight.

J Granules (GR, FG, GG, MG)

0.5 parts by weight of active compound are ground finely and associated with 99.5 parts by weight of carriers. Current methods here are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted with an active compound content of 0.5% by weight.

K ULV Solutions (UL)

10 parts by weight of active compound are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product to be applied undiluted with an active compound content of 10% by weight.

The compounds I or the herbicidal compositions comprising them can be applied pre- or post-emergence, or together with the seed of a crop plant. It is also possible to apply the herbicidal compositions or active compounds by applying seed, pretreated with the herbicidal compositions or active compounds, of a crop plant. If the active compounds are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spraying equipment, in such a way that as far as possible they do not come into contact with the leaves of the sensitive crop plants, while the active compounds reach the leaves of undesirable plants growing underneath, or the bare soil surface (post-directed, lay-by).

In a further embodiment, the compounds of the formula I or the herbicidal compositions can be applied by treating seed.

The treatment of seed comprises essentially all procedures familiar to the person skilled in the art (seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping and seed pelleting) based on the compounds of the formula I according to the invention or the compositions prepared therefrom. Here, the herbicidal compositions can be applied diluted or undiluted.

The term seed comprises seed of all types, such as, for example, corns, seeds, fruits, tubers, cuttings and similar forms. Here, preferably, the term seed describes corns and seeds.

The seed used can be seed of the useful plants mentioned above, but also the seed of transgenic plants or plants obtained by customary breeding methods.

The rates of application of active compound are from 0.001 to 3.0, preferably 0.01 to 1.0, kg/ha of active substance (a.s.), depending on the control target, the season, the target plants and the growth stage. To treat the seed, the compounds I are generally employed in amounts of from 0.001 to 10 kg per 100 kg of seed.

It may also be advantageous to use the compounds of the formula I in combination with safeners. Safeners are chemical compounds which prevent or reduce damage to useful plants without substantially affecting the herbicidal action of the compounds of the formula I on unwanted plants. They can be used both before sowing (for example in the treatment of seed, or on cuttings or seedlings) and before or after the emergence of the useful plant. The safeners and the compounds of the formula I can be used simultaneously or in succession. Suitable safeners are, for example, (quinolin-8-oxy)acetic acids, 1-phenyl-5-haloalkyl-1H1,2,4-triazole-3-carboxylic acids, 1-phenyl-4,5-dihydro-5-alkyl-1H-pyrazole-3,5-dicarboxylic acids, 4,5-dihydro-5,5-diaryl-3-isoxazolecarboxylic acids, dichloroacetamides, alpha-oximinophenylacetonitriles, acetophenone oximes, 4,6-dihalo-2-phenylpyrimidines, N-[[4-(aminocarbonyl)phenyl]-sulfonyl]-2-benzamides, 1,8-naphthalic anhydride, 2-halo-4-(haloalkyl)-5-thiazole-carboxylic acids, phosphorothiolates and O-phenyl N-alkylcarbamates and their agriculturally useful salts and, provided that they have an acid function, their agriculturally useful derivatives, such as amides, esters and thioesters.

To broaden the activity spectrum and to obtain synergistic effects, the compounds of the formula I can be mixed and jointly applied with numerous representatives of other herbicidal or growth-regulating groups of active compounds or with safeners. Suitable mixing partners are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, aryloxy/heteroaryl-oxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2-(hetaroyl/aroyl)-1,3-cyclohexanediones, heteroaryl aryl ketones, benzylisoxazolidinones, meta-CF₃-phenyl derivatives, carbamates, quinoline carboxylic acid and its derivatives, chloroacetanilides, cyclohexenone oxime ether derivates, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and heteroaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides, uracils and also phenylpyrazolines and isoxazolines and their derivatives.

Moreover, it may be useful to apply the compounds I alone or in combination with other herbicides or else also mixed with further crop protection agents, jointly, for example with compositions for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions which are employed for alleviating nutritional and trace element deficiencies. Other additives such as nonphytotoxic oils and oil concentrates may also be added.

Examples of herbicides which can be used in combination with the pyridine compounds of the formula I according to the present invention are:

b1) from the group of the lipid biosynthesis inhibitors:

alloxydim, alloxydim-sodium, butroxydim, clethodim, clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim, tralkoxydim, benfuresate, butylate, cycloate, dalapon, dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate;

b2) from the group of the ALS inhibitors:

amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, bispyribac, bispyribac-sodium, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cloransulam, cloransulam-methyl, cyclosulfamuron, diclosulam, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, florasulam, flucarbazone, flucarbazone-sodium, flucetosulfuron, flumetsulam, flupyrsulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, mesosulfuron, metosulam, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, penoxsulam, primisulfuron, primisulfuron-methyl, propoxycarbazone, propoxycarbazone-sodium, prosulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, pyribenzoxim, pyrimisulfan, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, pyroxsulam, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron, triflusulfuron-methyl and tritosulfuron;

b3) from the group of the photosynthesis inhibitors:

ametryn, amicarbazone, atrazine, bentazone, bentazone-sodium, bromacil, bromofenoxim, bromoxynil and its salts and esters, chlorobromuron, chloridazone, chlorotoluron, chloroxuron, cyanazine, desmedipham, desmetryn, dimefuron, dimethametryn, diquat, diquat-dibromide, diuron, fluometuron, hexazinone, ioxynil and its salts and esters, isoproturon, isouron, karbutilate, lenacil, linuron, metamitron, methabenzthiazuron, metobenzuron, metoxuron, metribuzin, monolinuron, neburon, paraquat, paraquat-dichloride, paraquat-dimetilsulfate, pentanochlor, phenmedipham, phenmedipham-ethyl, prometon, prometryn, propanil, propazine, pyridafol, pyridate, siduron, simazine, simetryn, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, thidiazuron and trietazine;

b4) from the group of the protoporphyrinogen-IX oxidase inhibitors:

acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, cinidon-ethyl, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, 2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-[(2H)-pyrimidinyl]-4-fluoro-N-Risopropyl)-methylsulfamoyl]benzamide (B-1; CAS 372137-35-4), ethyl[3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate (B-2; CAS 353292-31-6), N-ethyl-3-(2,6-dichloro-4-trifluoro-methylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (B-3; CAS 452098-92-9), N-tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (B-4; CAS 915396-43-9), N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethyl-phenoxy)-5-methyl-1H-pyrazole-1-carboxamide (B-5; CAS 452099-05-7) and N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (B-6; CAS 45100-03-7);

b5) from the group of the bleacher herbicides:

aclonifen, amitrol, beflubutamid, benzobicyclon, benzofenap, clomazone, diflufenican, fluridone, fluorochloridone, flurtamone, isoxaflutole, mesotrione, norflurazon, picolinafen, pyrasulfutole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, topramezone, 4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridyl]carbonyl]bicyclo[3.2.1]oct-3-en-2-one (B-7; CAS 352010-68-5) and 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine (B-8; CAS 180608-33-7);

b6) from the group of the EPSP synthase inhibitors: glyphosate, glyphosate-isopropylammonium and glyphosate-trimesium (sulfosate);

b7) from the group of the glutamine synthase inhibitors:

bilanaphos (bialaphos), bilanaphos-sodium, glufosinate and glufosinate-ammonium;

b8) from the group of the DHP synthase inhibitors: asulam;

b9) from the group of the mitose inhibitors:

amiprophos, amiprophos-methyl, benfluralin, butamiphos, butralin, carbetamide, chlorpropham, chlorthal, chlorthal-dimethyl, dinitramine, dithiopyr, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine, propham, propyzamide, tebutam, thiazopyr and trifluralin;

b10) from the group of the VLCFA inhibitors:

acetochlor, alachlor, anilofos, butachlor, cafenstrole, dimethachlor, dimethanamid, dimethenamid-P, diphenamid, fentrazamide, flufenacet, mefenacet, metazachlor, metolachlor, metolachlor-S, naproanilide, napropamide, pethoxamid, piperophos, pretilachlor, propachlor, propisochlor, pyroxasulfone (KIH-485) and thenylchlor;

Compounds of the formula 2:

in which the variables have the following meanings: Y is phenyl or 5- or 6-membered heteroaryl as defined at the outset, which radicals may be substituted by one to three groups R^(aa); R²¹, R²², R²³, R²⁴ are H, halogen or C₁-C₄-alkyl; X is O or NH; N is 0 or 1.

Compounds of the formula 2 have in particular the following meanings:

Y is

where # denotes the bond to the skeleton of the molecule; and R²¹, R²², R²³, R²⁴ are H, Cl, F or CH₃; R²⁵ is halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl; R²⁶ is C₁-C₄-alkyl; R²⁷ is halogen, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy; R²⁸ is H, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl or C₁-C₄-haloalkoxy; M is 0, 1, 2 or 3; X is oxygen; N is 0 or 1.

Preferred compounds of the formula 2 have the following meanings:

Y is

R²¹ is H; R²², R²³ are F; R²⁴ is H or F; X is oxygen; N is 0 or 1.

Particularly preferred compounds of the formula 2 are: 3-[5-(2,2-difluoroethoxy)-1-methyl-3-trifluoromethyl-1H-pyrazol-4-ylmethane-sulfonyl]-4-fluoro-5,5-dimethyl-4,5-dihydroisoxazole (2-1); 3-{[5-(2,2-difluoro-ethoxy)-1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl]fluoromethanesulfonyl}-5,5-dimethyl-4,5-dihydroisoxazole (2-2); 4-(4-fluoro-5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonyl-methyl)-2-methyl-5-trifluoromethyl-2H-[1,2,3]triazole (2-3); 4-[(5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonyl)fluoromethyl]-2-methyl-5-trifluoromethyl-2H-[1,2,3]-triazole (2-4); 4-(5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonylmethyl)-2-methyl-5-trifluoro-methyl-2H-[1,2,3]-triazole (2-5); 3-{[5-(2,2-difluoroethoxy)-1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl]difluoromethanesulfonyl}-5,5-dimethyl-4,5-dihydroisoxazole (2-6); 4-[(5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonyl)difluoromethyl]-2-methyl-5-trifluoro-methyl-2H-[1,2,3]-triazole (2-7); 3-{[5-(2,2-difluoroethoxy)-1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl]difluoromethanesulfonyl}-4-fluoro-5,5-dimethyl-4,5-dihydroisoxazole (2-8); 4-[difluoro-(4-fluoro-5,5-dimethyl-4,5-dihydroisoxazole-3-sulfonyl)methyl]-2-methyl-5-trifluoromethyl-2H-[1,2,3]triazole (2-9);

b11) from the group of the cellulose biosynthesis inhibitors:

chlorthiamid, dichlobenil, flupoxam and isoxaben;

b12) from the group of the decoupler herbicides:

dinoseb, dinoterb and DNOC and its salts;

b13) from the group of the auxin herbicides:

2,4-D and its salts and esters, 2,4-DB and its salts and esters, aminopyralid and its salts such as aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, benazolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorpropand its salts and esters, dichlorprop-P and its salts and esters, fluoroxypyr, fluoroxypyr-butomethyl, fluoroxypyr-meptyl, MCPA and its salts and esters, MCPA-thioethyl, MCPB and its salts and esters, mecopropand its salts and esters, mecoprop-P and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, TBA (2,3,6) and its salts and esters, triclopyr and its salts and esters, and 5,6-dichloro-2-cyclopropyl-4-pyrimidinecarboxylic acid (B-9; CAS 858956-08-8) and its salts and esters;

b14) from the group of the auxin transport inhibitors: diflufenzopyr, diflufenzopyr-sodium, naptalam and naptalam-sodium;

b15) from the group of the other herbicides: bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, maleic hydrazide, mefluidide, metam, methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine, triaziflam, tridiphane and 6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinol (B-10; CAS 499223-49-3) and its salts and esters.

Examples of preferred safeners C are benoxacor, cloquintocet, cyometrinil, cyprosulfamide, dichlormid, dicyclonone, dietholate, fenchlorazole, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen, mefenpyr, mephenate, naphthalic anhydride, oxabetrinil, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (B-11; MON4660, CAS 71526-07-3) and 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (B-12; R-29148, CAS 52836-31-4).

The active compounds of groups b1) to b15) and the safeners C are known herbicides and safeners, see, for example, The Compendium of Pesticide Common Names (http://www.alanwood.net/pesticides/); B. Hock, C. Fedtke, R. R. Schmidt, Herbizide [Herbicides], Georg Thieme Verlag, Stuttgart, 1995. Further herbicidally active compounds are known from WO 96/26202, WO 97/41116, WO 97/41117, WO 97/41118, WO 01/83459 and WO 2008/074991 and from W. Kramer et al. (ed.) “Modern Crop Protection Compounds”, Vol. 1, Wiley VCH, 2007 and the literature quoted therein.

The invention also relates to compositions in the form of a crop protection composition formulated as a 1-component composition comprising an active compound combination comprising at least one pyridine compound of the formula I and at least one further active compound, preferably selected from the active compounds of groups b1 to b15, and at least one solid or liquid carrier and/or one or more surfactants and, if desired, one or more further auxiliaries customary for crop protection compositions.

The invention also relates to compositions in the form of a crop protection composition formulated as a 2-component composition comprising a first component comprising at least one pyridine compound of the formula I, a solid or liquid carrier and/or one or more surfactants and a second component comprising at least one further active compound selected from the active compounds of groups b1 to b15, a solid or liquid carrier and/or one or more surfactants, where additionally both components may also comprise further auxiliaries customary for crop protection compositions.

In binary compositions comprising at least one compound of the formula I as component A and at least one herbicide B, the weight ratio of the active compounds A:B is generally in the range of from 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1.

In binary compositions comprising at least one compound of the formula I as component A and at least one safener C, the weight ratio of the active compounds A:C is generally in the range of from 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1.

In ternary compositions comprising both at least one compound of the formula I as component A, at least one herbicide B and at least one safener C, the relative parts by weight of the components A:B are generally in the range of from 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1; the weight ratio of the components A:C is generally in the range of from 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1; and the weight ratio of the components B:C is generally in the range of from 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1. Preferably, the weight ratio of the components A+B to the component C is in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1.

Examples of particularly preferred compositions according to the invention comprising in each case one individualized compound of the formula I and one mixing partner or a mixing partner combination are given in Table B below.

A further aspect of the invention relates to the compositions B-1 to B-1235 listed in Table B below, where in each case one row of Table B corresponds to a herbicidal composition comprising one of the compounds of the formula I individualized in the above description (component 1) and the further active compound from groups b1) to b15) and/or safener C stated in each case in the row in question (component 2). The active compounds in the compositions described are in each case preferably present in synergistically effective amounts.

TABLE B Herbicide(s) B Safener C B-1 clodinafop-propargyl — B-2 cycloxydim — B-3 cyhalofop-butyl — B-4 fenoxaprop-P-ethyl — B-5 pinoxaden — B-6 profoxydim — B-7 tepraloxydim — B-8 tralkoxydim — B-9 esprocarb — B-10 prosulfocarb — B-11 thiobencarb — B-12 triallate — B-13 bensulfuron-methyl — B-14 bispyribac-sodium — B-15 cyclosulfamuron — B-16 flumetsulam — B-17 flupyrsulfuron-methyl-sodium — B-18 foramsulfuron — B-19 imazamox — B-20 imazapic — B-21 imazapyr — B-22 imazaquin — B-23 imazethapyr — B-24 imazosulfuron — B-25 iodosulfuron-methyl-sodium — B-26 mesosulfuron — B-27 nicosulfuron — B-28 penoxsulam — B-29 propoxycarbazone-sodium — B-30 pyrazosulfuron-ethyl — B-31 pyroxsulam — B-32 rimsulfuron — B-33 sulfosulfuron — B-34 thiencarbazone-methyl — B-35 tritosulfuron — B-36 2,4-D and its salts and esters — B-37 aminopyralid and its salts and esters — B-38 clopyralid and its salts and esters — B-39 dicamba and its salts and esters — B-40 fluroxypyr-meptyl — B-41 quinclorac — B-42 quinmerac — B-43 B-9 — B-44 diflufenzopyr — B-45 diflufenzopyr-sodium — B-46 clomazone — B-47 diflufenican — B-48 fluorochloridone — B-49 isoxaflutol — B-50 mesotrione — B-51 picolinafen — B-52 sulcotrione — B-53 tefuryltrione — B-54 tembotrione — B-55 topramezone — B-56 B-7 — B-57 atrazine — B-58 diuron — B-59 fluometuron — B-60 hexazinone — B-61 isoproturon — B-62 metribuzin — B-63 propanil — B-64 terbuthylazine — B-65 paraquat dichloride — B-66 flumioxazin — B-67 oxyfluorfen — B-68 saflufenacil — B-69 sulfentrazone — B-70 B-1 — B-71 B-2 — B-72 glyphosate — B-73 glyphosate-isopropylammonium — B-74 glyphosate-trimesium (sulfosate) — B-75 glufosinate — B-76 glufosinate-ammonium — B-77 pendimethalin — B-78 trifluralin — B-79 acetochlor — B-80 cafenstrole — B-81 dimethenamid-P — B-82 fentrazamide — B-83 flufenacet — B-84 mefenacet — B-85 metazachlor — B-86 metolachlor-S — B-87 pyroxasulfone — B-88 isoxaben — B-89 dymron — B-90 indanofan — B-91 oxaziclomefone — B-92 triaziflam — B-93 atrazine + B-1 — B-94 atrazine + glyphosate — B-95 atrazine + mesotrione — B-96 atrazine + nicosulfuron — B-97 atrazine + tembotrione — B-98 atrazine + topramezone — B-99 clomazone + glyphosate — B-100 diflufenican + clodinafop-propargyl — B-101 diflufenican + fenoxaprop-p-ethyl — B-102 diflufenican + flupyrsulfuron-methyl-sodium — B-103 diflufenican + glyphosate — B-104 diflufenican + mesosulfuron-methyl — B-105 diflufenican + pinoxaden — B-106 diflufenican + pyroxsulam — B-107 flumetsulam + glyphosate — B-108 flumioxazin + glyphosate — B-109 imazapic + glyphosate — B-110 imazethapyr + glyphosate — B-111 Isoxaflutol + B-1 — B-112 isoxaflutol + glyphosate — B-113 metazachlor + B-1 — B-114 metazachlor + glyphosate — B-115 metazachlor + mesotrione — B-116 metazachlor + nicosulfuron — B-117 metazachlor + terbuthylazin — B-118 metazachlor + topramezone — B-119 metribuzin + glyphosate — B-120 pendimethalin + B-1 — B-121 pendimethalin + clodinafop-propargyl — B-122 pendimethalin + fenoxaprop-P-ethyl — B-123 pendimethalin + flupyrsulfuron-methyl-sodium — B-124 pendimethalin + glyphosate — B-125 pendimethalin + mesosulfuron-methyl — B-126 pendimethalin + mesotrionee — B-127 pendimethalin + nicosulfuron — B-128 pendimethalin + pinoxaden — B-129 pendimethalin + pyroxsulam — B-130 pendimethalin + tembotrione — B-131 pendimethalin + topramezone — B-132 pyroxasulfone + tembotrione — B-133 pyroxasulfone + topramezone — B-134 sulfentrazone + glyphosate — B-135 terbuthylazin + B-1 — B-136 terbuthylazin + foramsulfuron — B-137 terbuthylazin + glyphosate — B-138 terbuthylazin + mesotrione — B-139 terbuthylazin + nicosulfuron — B-140 terbuthylazin + tembotrione — B-141 terbuthylazin + topramezone — B-142 trifluralin + glyphosate — B-143 — benoxacor B-144 — cloquintocet B-145 — cyprosulfamide B-146 — dichlormid B-147 — fenchlorazole B-148 — isoxadifen B-149 — mefenpyr B-150 — B-11 B-151 — B-12 B-152 clodinafop-propargyl benoxacor B-153 cycloxydim benoxacor B-154 cyhalofop-butyl benoxacor B-155 fenoxaprop-P-ethyl benoxacor B-156 pinoxaden benoxacor B-157 profoxydim benoxacor B-158 tepraloxydim benoxacor B-159 tralkoxydim benoxacor B-160 esprocarb benoxacor B-161 prosulfocarb benoxacor B-162 thiobencarb benoxacor B-163 triallate benoxacor B-164 bensulfuron-methyl benoxacor B-165 bispyribac-sodium benoxacor B-166 cyclosulfamuron benoxacor B-167 flumetsulam benoxacor B-168 flupyrsulfuron-methyl-sodium benoxacor B-169 foramsulfuron benoxacor B-170 imazamox benoxacor B-171 imazapic benoxacor B-172 imazapyr benoxacor B-173 imazaquin benoxacor B-174 imazethapyr benoxacor B-175 imazosulfuron benoxacor B-176 iodosulfuron-methyl-sodium benoxacor B-177 mesosulfuron benoxacor B-178 nicosulfuron benoxacor B-179 penoxsulam benoxacor B-180 propoxycarbazone-sodium benoxacor B-181 pyrazosulfuron-ethyl benoxacor B-182 pyroxsulam benoxacor B-183 rimsulfuron benoxacor B-184 sulfosulfuron benoxacor B-185 thiencarbazone-methyl benoxacor B-186 tritosulfuron benoxacor B-187 2,4-D and its salts and esters benoxacor B-188 aminopyralid and its salts and esters benoxacor B-189 clopyralid and its salts and esters benoxacor B-190 dicamba and its salts and esters benoxacor B-191 fluroxypyr-meptyl benoxacor B-192 quinclorac benoxacor B-193 quinmerac benoxacor B-194 B-9 benoxacor B-195 diflufenzopyr benoxacor B-196 diflufenzopyr-sodium benoxacor B-197 clomazone benoxacor B-198 diflufenican benoxacor B-199 fluorochloridone benoxacor B-200 isoxaflutol benoxacor B-201 mesotrione benoxacor B-202 picolinafen benoxacor B-203 sulcotrione benoxacor B-204 tefuryltrione benoxacor B-205 tembotrione benoxacor B-206 topramezone benoxacor B-207 B-7 benoxacor B-208 atrazine benoxacor B-209 diuron benoxacor B-210 fluometuron benoxacor B-211 hexazinone benoxacor B-212 isoproturon benoxacor B-213 metribuzin benoxacor B-214 propanil benoxacor B-215 terbuthylazin benoxacor B-216 paraquat dichloride benoxacor B-217 flumioxazin benoxacor B-218 oxyfluorfen benoxacor B-219 saflufenacil benoxacor B-220 sulfentrazone benoxacor B-221 B-1 benoxacor B-222 B-2 benoxacor B-223 glyphosate benoxacor B-224 glyphosate-isopropylammonium benoxacor B-225 glyphosate-trimesium (sulfosate) benoxacor B-226 glufosinate benoxacor B-227 glufosinate-ammonium benoxacor B-228 pendimethalin benoxacor B-229 trifluralin benoxacor B-230 acetochlor benoxacor B-231 cafenstrole benoxacor B-232 dimethenamid-P benoxacor B-233 fentrazamide benoxacor B-234 flufenacet benoxacor B-235 mefenacet benoxacor B-236 metazachlor benoxacor B-237 metolachlor-S benoxacor B-238 pyroxasulfone benoxacor B-239 isoxaben benoxacor B-240 dymron benoxacor B-241 indanofan benoxacor B-242 oxaziclomefone benoxacor B-243 triaziflam benoxacor B-244 atrazine + B-1 benoxacor B-245 atrazine + glyphosate benoxacor B-246 atrazine + mesotrione benoxacor B-247 atrazine + nicosulfuron benoxacor B-248 atrazine + tembotrione benoxacor B-249 atrazine + topramezone benoxacor B-250 clomazone + glyphosate benoxacor B-251 diflufenican + clodinafop-propargyl benoxacor B-252 diflufenican + fenoxaprop-P-ethyl benoxacor B-253 diflufenican + flupyrsulfuron-methyl-sodium benoxacor B-254 diflufenican + glyphosate benoxacor B-255 diflufenican + mesosulfuron-methyl benoxacor B-256 diflufenican + pinoxaden benoxacor B-257 diflufenican + pyroxsulam benoxacor B-258 flumetsulam + glyphosate benoxacor B-259 flumioxazin + glyphosate benoxacor B-260 imazapic + glyphosate benoxacor B-261 imazethapyr + glyphosate benoxacor B-262 isoxaflutol + B-1 benoxacor B-263 isoxaflutol + glyphosate benoxacor B-264 metazachlor + B-1 benoxacor B-265 metazachlor + glyphosate benoxacor B-266 metazachlor + mesotrione benoxacor B-267 metazachlor + nicosulfuron benoxacor B-268 metazachlor + terbuthylazin benoxacor B-269 metazachlor + topramezone benoxacor B-270 metribuzin + glyphosate benoxacor B-271 pendimethalin + B-1 benoxacor B-272 pendimethalin + clodinafop-propargyl benoxacor B-273 pendimethalin + fenoxaprop-P-ethyl benoxacor B-274 pendimethalin + flupyrsulfuron-methyl-sodium benoxacor B-275 pendimethalin + glyphosate benoxacor B-276 pendimethalin + mesosulfuron-methyl benoxacor B-277 pendimethalin + mesotrionee benoxacor B-278 pendimethalin + nicosulfuron benoxacor B-279 pendimethalin + pinoxaden benoxacor B-280 pendimethalin + pyroxsulam benoxacor B-281 pendimethalin + tembotrione benoxacor B-282 pendimethalin + topramezone benoxacor B-283 pyroxasulfone + tembotrione benoxacor B-284 pyroxasulfone + topramezone benoxacor B-285 sulfentrazone + glyphosate benoxacor B-286 terbuthylazin + B-1 benoxacor B-287 terbuthylazin + foramsulfuron benoxacor B-288 terbuthylazin + glyphosate benoxacor B-289 terbuthylazin + mesotrione benoxacor B-290 terbuthylazin + nicosulfuron benoxacor B-291 terbuthylazin + tembotrione benoxacor B-292 terbuthylazin + topramezone benoxacor B-293 trifluralin + glyphosate benoxacor B-294 clodinafop-propargyl cloquintocet B-295 cycloxydim cloquintocet B-296 cyhalofop-butyl cloquintocet B-297 fenoxaprop-P-ethyl cloquintocet B-298 pinoxaden cloquintocet B-299 profoxydim cloquintocet B-300 tepraloxydim cloquintocet B-301 tralkoxydim cloquintocet B-302 esprocarb cloquintocet B-303 prosulfocarb cloquintocet B-304 thiobencarb cloquintocet B-305 triallate cloquintocet B-306 bensulfuron-methyl cloquintocet B-307 bispyribac-sodium cloquintocet B-308 cyclosulfamuron cloquintocet B-309 flumetsulam cloquintocet B-310 flupyrsulfuron-methyl-sodium cloquintocet B-311 foramsulfuron cloquintocet B-312 imazamox cloquintocet B-313 imazapic cloquintocet B-314 imazapyr cloquintocet B-315 imazaquin cloquintocet B-316 imazethapyr cloquintocet B-317 imazosulfuron cloquintocet B-318 iodosulfuron-methyl-sodium cloquintocet B-319 mesosulfuron cloquintocet B-320 nicosulfuron cloquintocet B-321 penoxsulam cloquintocet B-322 propoxycarbazone-sodium cloquintocet B-323 pyrazosulfuron-ethyl cloquintocet B-324 pyroxsulam cloquintocet B-325 rimsulfuron cloquintocet B-326 sulfosulfuron cloquintocet B-327 thiencarbazone-methyl cloquintocet B-328 tritosulfuron cloquintocet B-329 2,4-D and its salts and esters cloquintocet B-330 aminopyralid and its salts and esters cloquintocet B-331 clopyralid and its salts and esters cloquintocet B-332 dicamba and its salts and esters cloquintocet B-333 fluroxypyr-meptyl cloquintocet B-334 quinclorac cloquintocet B-335 quinmerac cloquintocet B-336 B-9 cloquintocet B-337 diflufenzopyr cloquintocet B-338 diflufenzopyr-sodium cloquintocet B-339 clomazone cloquintocet B-340 diflufenican cloquintocet B-341 fluorochloridone cloquintocet B-342 isoxaflutol cloquintocet B-343 mesotrione cloquintocet B-344 picolinafen cloquintocet B-345 sulcotrione cloquintocet B-346 tefuryltrione cloquintocet B-347 tembotrione cloquintocet B-348 topramezone cloquintocet B-349 B-7 cloquintocet B-350 atrazine cloquintocet B-351 diuron cloquintocet B-352 fluometuron cloquintocet B-353 hexazinone cloquintocet B-354 isoproturon cloquintocet B-355 metribuzin cloquintocet B-356 propanil cloquintocet B-357 terbuthylazin cloquintocet B-358 paraquat dichloride cloquintocet B-359 flumioxazin cloquintocet B-360 oxyfluorfen cloquintocet B-361 saflufenacil cloquintocet B-362 sulfentrazone cloquintocet B-363 B-1 cloquintocet B-364 B-2 cloquintocet B-365 glyphosate cloquintocet B-366 glyphosate-isopropylammonium cloquintocet B-367 glyphosate-trimesium (sulfosate) cloquintocet B-368 glufosinate cloquintocet B-369 glufosinate-ammonium cloquintocet B-370 pendimethalin cloquintocet B-371 trifluralin cloquintocet B-372 acetochlor cloquintocet B-373 cafenstrole cloquintocet B-374 dimethenamid-P cloquintocet B-375 fentrazamide cloquintocet B-376 flufenacet cloquintocet B-377 mefenacet cloquintocet B-378 metazachlor cloquintocet B-379 metolachlor-S cloquintocet B-380 pyroxasulfone cloquintocet B-381 isoxaben cloquintocet B-382 dymron cloquintocet B-383 indanofan cloquintocet B-384 oxaziclomefone cloquintocet B-385 triaziflam cloquintocet B-386 atrazine + B-1 cloquintocet B-387 atrazine + glyphosate cloquintocet B-388 atrazine + mesotrione cloquintocet B-389 atrazine + nicosulfuron cloquintocet B-390 atrazine + tembotrione cloquintocet B-391 atrazine + topramezone cloquintocet B-392 clomazone + glyphosate cloquintocet B-393 diflufenican + clodinafop-propargyl cloquintocet B-394 diflufenican + fenoxaprop-p-ethyl cloquintocet B-395 diflufenican + flupyrsulfuron-methyl-sodium cloquintocet B-396 diflufenican + glyphosate cloquintocet B-397 diflufenican + mesosulfuron-methyl cloquintocet B-398 diflufenican + pinoxaden cloquintocet B-399 diflufenican + pyroxsulam cloquintocet B-400 flumetsulam + glyphosate cloquintocet B-401 flumioxazin + glyphosate cloquintocet B-402 imazapic + glyphosate cloquintocet B-403 imazethapyr + glyphosate cloquintocet B-404 isoxaflutol + B-1 cloquintocet B-405 isoxaflutol + glyphosate cloquintocet B-406 metazachlor + B-1 cloquintocet B-407 metazachlor + glyphosate cloquintocet B-408 metazachlor + mesotrione cloquintocet B-409 metazachlor + nicosulfuron cloquintocet B-410 metazachlor + terbuthylazin cloquintocet B-411 metazachlor + topramezone cloquintocet B-412 metribuzin + glyphosate cloquintocet B-413 pendimethalin + B-1 cloquintocet B-414 pendimethalin + clodinafop-propargyl cloquintocet B-415 pendimethalin + fenoxaprop-P-ethyl cloquintocet B-416 pendimethalin + flupyrsulfuron-methyl-sodium cloquintocet B-417 pendimethalin + glyphosate cloquintocet B-418 pendimethalin + mesosulfuron-methyl cloquintocet B-419 pendimethalin + mesotrione cloquintocet B-420 pendimethalin + nicosulfuron cloquintocet B-421 pendimethalin + pinoxaden cloquintocet B-422 pendimethalin + pyroxsulam cloquintocet B-423 pendimethalin + tembotrione cloquintocet B-424 pendimethalin + topramezone cloquintocet B-425 pyroxasulfone + tembotrione cloquintocet B-426 pyroxasulfone + topramezone cloquintocet B-427 sulfentrazone + glyphosate cloquintocet B-428 terbuthylazin + B-1 cloquintocet B-429 terbuthylazin + foramsulfuron cloquintocet B-430 terbuthylazin + glyphosate cloquintocet B-431 terbuthylazin + mesotrione cloquintocet B-432 terbuthylazin + nicosulfuron cloquintocet B-433 terbuthylazin + tembotrione cloquintocet B-434 terbuthylazin + topramezone cloquintocet B-435 trifluralin + glyphosate cloquintocet B-436 clodinafop-propargyl dichlormid B-437 cycloxydim dichlormid B-438 cyhalofop-butyl dichlormid B-439 fenoxaprop-P-ethyl dichlormid B-440 pinoxaden dichlormid B-441 profoxydim dichlormid B-442 tepraloxydim dichlormid B-443 tralkoxydim dichlormid B-444 esprocarb dichlormid B-445 prosulfocarb dichlormid B-446 thiobencarb dichlormid B-447 triallate dichlormid B-448 bensulfuron-methyl dichlormid B-449 bispyribac-sodium dichlormid B-450 cyclosulfamuron dichlormid B-451 flumetsulam dichlormid B-452 flupyrsulfuron-methyl-sodium dichlormid B-453 foramsulfuron dichlormid B-454 imazamox dichlormid B-455 imazapic dichlormid B-456 imazapyr dichlormid B-457 imazaquin dichlormid B-458 imazethapyr dichlormid B-459 imazosulfuron dichlormid B-460 iodosulfuron-methyl-sodium dichlormid B-461 mesosulfuron dichlormid B-462 nicosulfuron dichlormid B-463 penoxsulam dichlormid B-464 propoxycarbazone-sodium dichlormid B-465 pyrazosulfuron-ethyl dichlormid B-466 pyroxsulam dichlormid B-467 rimsulfuron dichlormid B-468 sulfosulfuron dichlormid B-469 thiencarbazone-methyl dichlormid B-470 tritosulfuron dichlormid B-471 2,4-D and its salts and esters dichlormid B-472 aminopyralid and its salts and esters dichlormid B-473 clopyralid and its salts and esters dichlormid B-474 dicamba and its salts and esters dichlormid B-475 fluroxypyr-meptyl dichlormid B-476 quinclorac dichlormid B-477 quinmerac dichlormid B-478 B-9 dichlormid B-479 diflufenzopyr dichlormid B-480 diflufenzopyr-sodium dichlormid B-481 clomazone dichlormid B-482 diflufenican dichlormid B-483 fluorochloridone dichlormid B-484 isoxaflutol dichlormid B-485 mesotrione dichlormid B-486 picolinafen dichlormid B-487 sulcotrione dichlormid B-488 tefuryltrione dichlormid B-489 tembotrione dichlormid B-490 topramezone dichlormid B-491 B-7 dichlormid B-492 atrazine dichlormid B-493 diuron dichlormid B-494 fluometuron dichlormid B-495 hexazinone dichlormid B-496 isoproturon dichlormid B-497 metribuzin dichlormid B-498 propanil dichlormid B-499 terbuthylazin dichlormid B-500 paraquat dichloride dichlormid B-501 flumioxazin dichlormid B-502 oxyfluorfen dichlormid B-503 saflufenacil dichlormid B-504 sulfentrazone dichlormid B-505 B-1 dichlormid B-506 B-2 dichlormid B-507 glyphosate dichlormid B-508 glyphosate-isopropylammonium dichlormid B-509 glyphosate-trimesium (sulfosate) dichlormid B-510 glufosinate dichlormid B-511 glufosinate-ammonium dichlormid B-512 pendimethalin dichlormid B-513 trifluralin dichlormid B-514 acetochlor dichlormid B-515 cafenstrole dichlormid B-516 dimethenamid-P dichlormid B-517 fentrazamide dichlormid B-518 flufenacet dichlormid B-519 mefenacet dichlormid B-520 metazachlor dichlormid B-521 metolachlor-S dichlormid B-522 pyroxasulfone dichlormid B-523 isoxaben dichlormid B-524 dymron dichlormid B-525 indanofan dichlormid B-526 oxaziclomefone dichlormid B-527 triaziflam dichlormid B-528 atrazine + B-1 dichlormid B-529 atrazine + glyphosate dichlormid B-530 atrazine + mesotrione dichlormid B-531 atrazine + nicosulfuron dichlormid B-532 atrazine + tembotrione dichlormid B-533 atrazine + topramezone dichlormid B-534 clomazone + glyphosate dichlormid B-535 diflufenican + clodinafop-propargyl dichlormid B-536 diflufenican + fenoxaprop-p-ethyl dichlormid B-537 diflufenican + flupyrsulfuron-methyl-sodium dichlormid B-538 diflufenican + glyphosate dichlormid B-539 diflufenican + mesosulfuron-methyl dichlormid B-540 diflufenican + pinoxaden dichlormid B-541 diflufenican + pyroxsulam dichlormid B-542 flumetsulam + glyphosate dichlormid B-543 flumioxazin + glyphosate dichlormid B-544 imazapic + glyphosate dichlormid B-545 imazethapyr + glyphosate dichlormid B-546 isoxaflutol + B-1 dichlormid B-547 isoxaflutol + glyphosate dichlormid B-548 metazachlor + B-1 dichlormid B-549 metazachlor + glyphosate dichlormid B-550 metazachlor + mesotrione dichlormid B-551 metazachlor + nicosulfuron dichlormid B-552 metazachlor + terbuthylazin dichlormid B-553 metazachlor + topramezone dichlormid B-554 metribuzin + glyphosate dichlormid B-555 pendimethalin + B-1 dichlormid B-556 pendimethalin + clodinafop-propargyl dichlormid B-557 pendimethalin + fenoxaprop-P-ethyl dichlormid B-558 pendimethalin + flupyrsulfuron-methyl-sodium dichlormid B-559 pendimethalin + glyphosate dichlormid B-560 pendimethalin + mesosulfuron-methyl dichlormid B-561 pendimethalin + mesotrione dichlormid B-562 pendimethalin + nicosulfuron dichlormid B-563 pendimethalin + pinoxaden dichlormid B-564 pendimethalin + pyroxsulam dichlormid B-565 pendimethalin + tembotrione dichlormid B-566 pendimethalin + topramezone dichlormid B-567 pyroxasulfone + tembotrione dichlormid B-568 pyroxasulfone + topramezone dichlormid B-569 sulfentrazone + glyphosate dichlormid B-570 ferbuthylazin + B-1 dichlormid B-571 terbuthylazin + foramsulfuron dichlormid B-572 terbuthylazin + glyphosate dichlormid B-573 terbuthylazin + mesotrione dichlormid B-574 terbuthylazin + nicosulfuron dichlormid B-575 terbuthylazin + tembotrione dichlormid B-576 terbuthylazin + topramezone dichlormid B-577 trifluralin + glyphosate dichlormid B-578 clodinafop-propargyl fenchlorazole B-579 cycloxydim fenchlorazole B-580 cyhalofop-butyl fenchlorazole B-581 fenoxaprop-P-ethyl fenchlorazole B-582 pinoxaden fenchlorazole B-583 profoxydim fenchlorazole B-584 tepraloxydim fenchlorazole B-585 tralkoxydim fenchlorazole B-586 esprocarb fenchlorazole B-587 prosulfocarb fenchlorazole B-588 thiobencarb fenchlorazole B-589 triallate fenchlorazole B-590 bensulfuron-methyl fenchlorazole B-591 bispyribac-sodium fenchlorazole B-592 cyclosulfamuron fenchlorazole B-593 flumetsulam fenchlorazole B-594 flupyrsulfuron-methyl-sodium fenchlorazole B-595 foramsulfuron fenchlorazole B-596 imazamox fenchlorazole B-597 imazapic fenchlorazole B-598 imazapyr fenchlorazole B-599 imazaquin fenchlorazole B-600 imazethapyr fenchlorazole B-601 imazosulfuron fenchlorazole B-602 iodosulfuron-methyl-sodium fenchlorazole B-603 mesosulfuron fenchlorazole B-604 nicosulfuron fenchlorazole B-605 penoxsulam fenchlorazole B-606 propoxycarbazone-sodium fenchlorazole B-607 pyrazosulfuron-ethyl fenchlorazole B-608 pyroxsulam fenchlorazole B-609 rimsulfuron fenchlorazole B-610 sulfosulfuron fenchlorazole B-611 thiencarbazone-methyl fenchlorazole B-612 tritosulfuron fenchlorazole B-613 2,4-D and its salts and esters fenchlorazole B-614 aminopyralid and its salts and esters fenchlorazole B-615 clopyralid and its salts and esters fenchlorazole B-616 dicamba and its salts and esters fenchlorazole B-617 fluroxypyr-meptyl fenchlorazole B-618 quinclorac fenchlorazole B-619 quinmerac fenchlorazole B-620 B-9 fenchlorazole B-621 diflufenzopyr fenchlorazole B-622 diflufenzopyr-sodium fenchlorazole B-623 clomazone fenchlorazole B-624 diflufenican fenchlorazole B-625 fluorochloridone fenchlorazole B-626 isoxaflutol fenchlorazole B-627 mesotrione fenchlorazole B-628 picolinafen fenchlorazole B-629 sulcotrione fenchlorazole B-630 tefuryltrione fenchlorazole B-631 tembotrione fenchlorazole B-632 topramezone fenchlorazole B-633 B-7 fenchlorazole B-634 atrazine fenchlorazole B-635 diuron fenchlorazole B-636 fluometuron fenchlorazole B-637 hexazinone fenchlorazole B-638 isoproturon fenchlorazole B-639 metribuzin fenchlorazole B-640 propanil fenchlorazole B-641 terbuthylazin fenchlorazole B-642 paraquat dichloride fenchlorazole B-643 flumioxazin fenchlorazole B-644 oxyfluorfen fenchlorazole B-645 saflufenacil fenchlorazole B-646 sulfentrazone fenchlorazole B-647 B-1 fenchlorazole B-648 B-2 fenchlorazole B-649 glyphosate fenchlorazole B-650 glyphosate-isopropylammonium fenchlorazole B-651 glyphosate-trimesium (sulfosate) fenchlorazole B-652 glufosinate fenchlorazole B-653 glufosinate-ammonium fenchlorazole B-654 pendimethalin fenchlorazole B-655 trifluralin fenchlorazole B-656 acetochlor fenchlorazole B-657 cafenstrole fenchlorazole B-658 dimethenamid-P fenchlorazole B-659 fentrazamide fenchlorazole B-660 flufenacet fenchlorazole B-661 mefenacet fenchlorazole B-662 metazachlor fenchlorazole B-663 metolachlor-S fenchlorazole B-664 pyroxasulfone fenchlorazole B-665 isoxaben fenchlorazole B-666 dymron fenchlorazole B-667 indanofan fenchlorazole B-668 oxaziclomefone fenchlorazole B-669 friaziflam fenchlorazole B-670 atrazine + B-1 fenchlorazole B-671 atrazine + glyphosate fenchlorazole B-672 atrazine + mesotrione fenchlorazole B-673 atrazine + nicosulfuron fenchlorazole B-674 atrazine + tembotrione fenchlorazole B-675 atrazine + topramezone fenchlorazole B-676 clomazone + glyphosate fenchlorazole B-677 diflufenican + clodinafop-propargyl fenchlorazole B-678 diflufenican + fenoxaprop-P-ethyl fenchlorazole B-679 diflufenican + flupyrsulfuron-methyl-sodium fenchlorazole B-680 diflufenican + glyphosate fenchlorazole B-681 diflufenican + mesosulfuron-methyl fenchlorazole B-682 diflufenican + pinoxaden fenchlorazole B-683 diflufenican + pyroxsulam fenchlorazole B-684 flumetsulam + glyphosate fenchlorazole B-685 flumioxazin + glyphosate fenchlorazole B-686 imazapic + glyphosate fenchlorazole B-687 imazethapyr + glyphosate fenchlorazole B-688 isoxaflutol + B-1 fenchlorazole B-689 isoxaflutol + glyphosate fenchlorazole B-690 metazachlor + B-1 fenchlorazole B-691 metazachlor + glyphosate fenchlorazole B-692 metazachlor + mesotrione fenchlorazole B-693 metazachlor + nicosulfuron fenchlorazole B-694 metazachlor + terbuthylazin fenchlorazole B-695 metazachlor + topramezone fenchlorazole B-696 metribuzin + glyphosate fenchlorazole B-697 pendimethalin + B-1 fenchlorazole B-698 pendimethalin + clodinafop-propargyl fenchlorazole B-699 pendimethalin + fenoxaprop-P-ethyl fenchlorazole B-700 pendimethalin + flupyrsulfuron-methyl-sodium fenchlorazole B-701 pendimethalin + glyphosate fenchlorazole B-702 pendimethalin + mesosulfuron-methyl fenchlorazole B-703 pendimethalin + mesotrione fenchlorazole B-704 pendimethalin + nicosulfuron fenchlorazole B-705 pendimethalin + pinoxaden fenchlorazole B-706 pendimethalin + pyroxsulam fenchlorazole B-707 pendimethalin + tembotrione fenchlorazole B-708 pendimethalin + topramezone fenchlorazole B-709 pyroxasulfone + tembotrione fenchlorazole B-710 pyroxasulfone + topramezone fenchlorazole B-711 sulfentrazone + glyphosate fenchlorazole B-712 terbuthylazin + B-1 fenchlorazole B-713 terbuthylazin + foramsulfuron fenchlorazole B-714 terbuthylazin + glyphosate fenchlorazole B-715 terbuthylazin + mesotrione fenchlorazole B-716 terbuthylazin + nicosulfuron fenchlorazole B-717 terbuthylazin + tembotrione fenchlorazole B-718 terbuthylazin + topramezone fenchlorazole B-719 trifluralin + glyphosate fenchlorazole B-720 clodinafop-propargyl isoxadifen B-721 cycloxydim isoxadifen B-722 cyhalofop-butyl isoxadifen B-723 fenoxaprop-P-ethyl isoxadifen B-724 pinoxaden isoxadifen B-725 profoxydim isoxadifen B-726 tepraloxydim isoxadifen B-727 tralkoxydim isoxadifen B-728 esprocarb isoxadifen B-729 prosulfocarb isoxadifen B-730 thiobencarb isoxadifen B-731 triallate isoxadifen B-732 bensulfuron-methyl isoxadifen B-733 bispyribac-sodium isoxadifen B-734 cyclosulfamuron isoxadifen B-735 flumetsulam isoxadifen B-736 flupyrsulfuron-methyl-sodium isoxadifen B-737 foramsulfuron isoxadifen B-738 imazamox isoxadifen B-739 imazapic isoxadifen B-740 imazapyr isoxadifen B-741 imazaquin isoxadifen B-742 imazethapyr isoxadifen B-743 imazosulfuron isoxadifen B-744 iodosulfuron-methyl-sodium isoxadifen B-745 mesosulfuron isoxadifen B-746 nicosulfuron isoxadifen B-747 penoxsulam isoxadifen B-748 propoxycarbazone-sodium isoxadifen B-749 pyrazosulfuron-ethyl isoxadifen B-750 pyroxsulam isoxadifen B-751 rimsulfuron isoxadifen B-752 sulfosulfuron isoxadifen B-753 thiencarbazone-methyl isoxadifen B-754 tritosulfuron isoxadifen B-755 2,4-D and its salts and esters isoxadifen B-756 aminopyralid and its salts and esters isoxadifen B-757 clopyralid and its salts and esters isoxadifen B-758 dicamba and its salts and esters isoxadifen B-759 fluroxypyr-meptyl isoxadifen B-760 quinclorac isoxadifen B-761 quinmerac isoxadifen B-762 B-9 isoxadifen B-763 diflufenzopyr isoxadifen B-764 diflufenzopyr-sodium isoxadifen B-765 clomazone isoxadifen B-766 diflufenican isoxadifen B-767 fluorochloridone isoxadifen B-768 isoxaflutol isoxadifen B-769 mesotrione isoxadifen B-770 picolinafen isoxadifen B-771 sulcotrione isoxadifen B-772 tefuryltrione isoxadifen B-773 tembotrione isoxadifen B-774 topramezone isoxadifen B-775 B-7 isoxadifen B-776 atrazine isoxadifen B-777 diuron isoxadifen B-778 fluometuron isoxadifen B-779 hexazinone isoxadifen B-780 isoproturon isoxadifen B-781 metribuzin isoxadifen B-782 propanil isoxadifen B-783 terbuthylazin isoxadifen B-784 paraquat dichloride isoxadifen B-785 flumioxazin isoxadifen B-786 oxyfluorfen isoxadifen B-787 saflufenacil isoxadifen B-788 sulfentrazone isoxadifen B-789 B-1 isoxadifen B-790 B-2 isoxadifen B-791 glyphosate isoxadifen B-792 glyphosate-isopropylammonium isoxadifen B-793 glyphosate-trimesium (sulfosate) isoxadifen B-794 glufosinate isoxadifen B-795 glufosinate-ammonium isoxadifen B-796 pendimethalin isoxadifen B-797 trifluralin isoxadifen B-798 acetochlor isoxadifen B-799 cafenstrole isoxadifen B-800 dimethenamid-P isoxadifen B-801 fentrazamide isoxadifen B-802 flufenacet isoxadifen B-803 mefenacet isoxadifen B-804 metazachlor isoxadifen B-805 metolachlor-S isoxadifen B-806 pyroxasulfone isoxadifen B-807 isoxaben isoxadifen B-808 dymron isoxadifen B-809 indanofan isoxadifen B-810 oxaziclomefone isoxadifen B-811 triaziflam isoxadifen B-812 atrazine + B-1 isoxadifen B-813 atrazine + glyphosate isoxadifen B-814 atrazine + mesotrione isoxadifen B-815 atrazine + nicosulfuron isoxadifen B-816 atrazine + tembotrione isoxadifen B-817 atrazine + topramezone isoxadifen B-818 clomazone + glyphosate isoxadifen B-819 diflufenican + clodinafop-propargyl isoxadifen B-820 diflufenican + fenoxaprop-P-ethyl isoxadifen B-821 diflufenican + flupyrsulfuron-methyl-sodium isoxadifen B-822 diflufenican + glyphosate isoxadifen B-823 diflufenican + mesosulfuron-methyl isoxadifen B-824 diflufenican + pinoxaden isoxadifen B-825 diflufenican + pyroxsulam isoxadifen B-826 flumetsulam + glyphosate isoxadifen B-827 flumioxazin + glyphosate isoxadifen B-828 imazapic + glyphosate isoxadifen B-829 imazethapyr + glyphosate isoxadifen B-830 isoxaflutol + B-1 isoxadifen B-831 isoxaflutol + glyphosate isoxadifen B-832 metazachlor + B-1 isoxadifen B-833 metazachlor + glyphosate isoxadifen B-834 metazachlor + mesotrione isoxadifen B-835 metazachlor + nicosulfuron isoxadifen B-836 metazachlor + terbuthylazin isoxadifen B-837 metazachlor + topramezone isoxadifen B-838 metribuzin + glyphosate isoxadifen B-839 pendimethalin + B-1 isoxadifen B-840 pendimethalin + clodinafop-propargyl isoxadifen B-841 pendimethalin + fenoxaprop-P-ethyl isoxadifen B-842 pendimethalin + flupyrsulfuron-methyl-sodium isoxadifen B-843 pendimethalin + glyphosate isoxadifen B-844 pendimethalin + mesosulfuron-methyl isoxadifen B-845 pendimethalin + mesotrione isoxadifen B-846 pendimethalin + nicosulfuron isoxadifen B-847 pendimethalin + pinoxaden isoxadifen B-848 pendimethalin + pyroxsulam isoxadifen B-849 pendimethalin + tembotrione isoxadifen B-850 pendimethalin + topramezone isoxadifen B-851 pyroxasulfone + tembotrione isoxadifen B-852 pyroxasulfone + topramezone isoxadifen B-853 sulfentrazone + glyphosate isoxadifen B-854 terbuthylazin + B-1 isoxadifen B-855 terbuthylazin + foramsulfuron isoxadifen B-856 terbuthylazin + glyphosate isoxadifen B-857 terbuthylazin + mesotrione isoxadifen B-858 terbuthylazin + nicosulfuron isoxadifen B-859 terbuthylazin + tembotrione isoxadifen B-860 terbuthylazin + topramezone isoxadifen B-861 trifluralin + glyphosate isoxadifen B-862 clodinafop-propargyl mefenpyr B-863 cycloxydim mefenpyr B-864 cyhalofop-butyl mefenpyr B-865 fenoxaprop-P-ethyl mefenpyr B-866 pinoxaden mefenpyr B-867 profoxydim mefenpyr B-868 tepraloxydim mefenpyr B-869 tralkoxydim mefenpyr B-870 esprocarb mefenpyr B-871 prosulfocarb mefenpyr B-872 thiobencarb mefenpyr B-873 triallate mefenpyr B-874 bensulfuron-methyl mefenpyr B-875 bispyribac-sodium mefenpyr B-876 cyclosulfamuron mefenpyr B-877 flumetsulam mefenpyr B-878 flupyrsulfuron-methyl-sodium mefenpyr B-879 foramsulfuron mefenpyr B-880 imazamox mefenpyr B-881 imazapic mefenpyr B-882 imazapyr mefenpyr B-883 imazaquin mefenpyr B-884 imazethapyr mefenpyr B-885 imazosulfuron mefenpyr B-886 iodosulfuron-methyl-sodium mefenpyr B-887 mesosulfuron mefenpyr B-888 nicosulfuron mefenpyr B-889 penoxsulam mefenpyr B-890 propoxycarbazone-sodium mefenpyr B-891 pyrazosulfuron-ethyl mefenpyr B-892 pyroxsulam mefenpyr B-893 rimsulfuron mefenpyr B-894 sulfosulfuron mefenpyr B-895 thiencarbazone-methyl mefenpyr B-896 tritosulfuron mefenpyr B-897 2,4-D and its salts and esters mefenpyr B-898 aminopyralid and its salts and esters mefenpyr B-899 clopyralid and its salts and esters mefenpyr B-900 dicamba and its salts and esters mefenpyr B-901 fluroxypyr-meptyl mefenpyr B-902 quinclorac mefenpyr B-903 quinmerac mefenpyr B-904 B-9 mefenpyr B-905 diflufenzopyr mefenpyr B-906 diflufenzopyr-sodium mefenpyr B-907 clomazone mefenpyr B-908 diflufenican mefenpyr B-909 fluorochloridone mefenpyr B-910 isoxaflutol mefenpyr B-911 mesotrione mefenpyr B-912 picolinafen mefenpyr B-913 sulcotrione mefenpyr B-914 tefuryltrione mefenpyr B-915 tembotrione mefenpyr B-916 topramezone mefenpyr B-917 B-7 mefenpyr B-918 atrazine mefenpyr B-919 diuron mefenpyr B-920 fluometuron mefenpyr B-921 hexazinone mefenpyr B-922 isoproturon mefenpyr B-923 metribuzin mefenpyr B-924 propanil mefenpyr B-925 terbuthylazin mefenpyr B-926 paraquat dichloride mefenpyr B-927 flumioxazin mefenpyr B-928 oxyfluorfen mefenpyr B-929 saflufenacil mefenpyr B-930 sulfentrazone mefenpyr B-931 B-1 mefenpyr B-932 B-2 mefenpyr B-933 glyphosate mefenpyr B-934 glyphosate-isopropylammonium mefenpyr B-935 glyphosate-trimesium (sulfosate) mefenpyr B-936 glufosinate mefenpyr B-937 glufosinate-ammonium mefenpyr B-938 pendimethalin mefenpyr B-939 trifluralin mefenpyr B-940 acetochlor mefenpyr B-941 cafenstrole mefenpyr B-942 dimethenamid-p mefenpyr B-943 fentrazamide mefenpyr B-944 flufenacet mefenpyr B-945 mefenacet mefenpyr B-946 metazachlor mefenpyr B-947 metolachlor-S mefenpyr B-948 pyroxasulfone mefenpyr B-949 isoxaben mefenpyr B-950 dymron mefenpyr B-951 indanofan mefenpyr B-952 oxaziclomefone mefenpyr B-953 triaziflam mefenpyr B-954 atrazine + B-1 mefenpyr B-955 atrazine + glyphosate mefenpyr B-956 atrazine + mesotrione mefenpyr B-957 atrazine + nicosulfuron mefenpyr B-958 atrazine + tembotrione mefenpyr B-959 atrazine + topramezone mefenpyr B-960 clomazone + glyphosate mefenpyr B-961 diflufenican + clodinafop-propargyl mefenpyr B-962 diflufenican + fenoxaprop-P-ethyl mefenpyr B-963 diflufenican + fiupyrsulfuron-methyl-sodium mefenpyr B-964 diflufenican + glyphosate mefenpyr B-965 diflufenican + mesosulfuron-methyl mefenpyr B-966 diflufenican + pinoxaden mefenpyr B-967 diflufenican + pyroxsulam mefenpyr B-968 flumetsulam + glyphosate mefenpyr B-969 flumioxazin + glyphosate mefenpyr B-970 imazapic + glyphosate mefenpyr B-971 imazethapyr + glyphosate mefenpyr B-972 isoxaflutol + B-1 mefenpyr B-973 isoxaflutol + glyphosate mefenpyr B-974 metazachlor + B-1 mefenpyr B-975 metazachlor + glyphosate mefenpyr B-976 metazachlor + mesotrione mefenpyr B-977 metazachlor + nicosulfuron mefenpyr B-978 metazachlor + terbuthylazin mefenpyr B-979 metazachlor + topramezone mefenpyr B-980 metribuzin + glyphosate mefenpyr B-981 pendimethalin + B-1 mefenpyr B-982 pendimethalin + clodinafop-propargyl mefenpyr B-983 pendimethalin + fenoxaprop-P-ethyl mefenpyr B-984 pendimethalin + flupyrsulfuron-methyl-sodium mefenpyr B-985 pendimethalin + glyphosate mefenpyr B-986 pendimethalin + mesosulfuron-methyl mefenpyr B-987 pendimethalin + mesotrione mefenpyr B-988 pendimethalin + nicosulfuron mefenpyr B-989 pendimethalin + pinoxaden mefenpyr B-990 pendimethalin + pyroxsulam mefenpyr B-991 pendimethalin + tembotrione mefenpyr B-992 pendimethalin + topramezone mefenpyr B-993 pyroxasulfone + tembotrione mefenpyr B-994 pyroxasulfone + topramezone mefenpyr B-995 sulfentrazone + glyphosate mefenpyr B-996 terbuthylazin + B-1 mefenpyr B-997 terbuthylazin + foramsulfuron mefenpyr B-998 terbuthylazin + glyphosate mefenpyr B-999 terbuthylazin + mesotrione mefenpyr B-1000 terbuthylazin + nicosulfuron mefenpyr B-1001 terbuthylazin + tembotrione mefenpyr B-1002 terbuthylazin + topramezone mefenpyr B-1003 trifluralin + glyphosate mefenpyr B-1004 clodinafop-propargyl B-12 B-1005 cycloxydim B-12 B-1006 cyhalofop-butyl B-12 B-1007 fenoxaprop-P-ethyl B-12 B-1008 pinoxaden B-12 B-1009 profoxydim B-12 B-1010 tepraloxydim B-12 B-1011 tralkoxydim B-12 B-1012 esprocarb B-12 B-1013 prosulfocarb B-12 B-1014 thiobencarb B-12 B-1015 triallate B-12 B-1016 bensulfuron-methyl B-12 B-1017 bispyribac-sodium B-12 B-1018 cyclosulfamuron B-12 B-1019 flumetsulam B-12 B-1020 flupyrsulfuron-methyl-sodium B-12 B-1021 foramsulfuron B-12 B-1022 imazamox B-12 B-1023 imazapic B-12 B-1024 imazapyr B-12 B-1025 imazaquin B-12 B-1026 imazethapyr B-12 B-1027 imazosulfuron B-12 B-1028 iodosulfuron-methyl-sodium B-12 B-1029 mesosulfuron B-12 B-1030 nicosulfuron B-12 B-1031 penoxsulam B-12 B-1032 propoxycarbazone-sodium B-12 B-1033 pyrazosulfuron-ethyl B-12 B-1034 pyroxsulam B-12 B-1035 rimsulfuron B-12 B-1036 sulfosulfuron B-12 B-1037 thiencarbazone-methyl B-12 B-1038 tritosulfuron B-12 B-1039 2,4-D and its salts and esters B-12 B-1040 aminopyralid and its salts and esters B-12 B-1041 clopyralid and its salts and esters B-12 B-1042 dicamba and its salts and esters B-12 B-1043 fluroxypyr-meptyl B-12 B-1044 quinclorac B-12 B-1045 quinmerac B-12 B-1046 B-9 B-12 B-1047 diflufenzopyr B-12 B-1048 diflufenzopyr-sodium B-12 B-1049 clomazone B-12 B-1050 diflufenican B-12 B-1051 fluorochloridone B-12 B-1052 isoxaflutol B-12 B-1053 mesotrione B-12 B-1054 picolinafen B-12 B-1055 sulcotrione B-12 B-1056 tefuryltrione B-12 B-1057 tembotrione B-12 B-1058 topramezone B-12 B-1059 B-7 B-12 B-1060 atrazine B-12 B-1061 diuron B-12 B-1062 fluometuron B-12 B-1063 hexazinone B-12 B-1064 isoproturon B-12 B-1065 metribuzin B-12 B-1066 propanil B-12 B-1067 terbuthylazin B-12 B-1068 paraquat dichloride B-12 B-1069 flumioxazin B-12 B-1070 oxyfluorfen B-12 B-1071 saflufenacil B-12 B-1072 sulfentrazone B-12 B-1073 B-1 B-12 B-1074 B-2 B-12 B-1075 glyphosate B-12 B-1076 glyphosate-isopropylammonium B-12 B-1077 glyphosate-trimesium (sulfosate) B-12 B-1078 glufosinate B-12 B-1079 glufosinate-ammonium B-12 B-1080 pendimethalin B-12 B-1081 trifluralin B-12 B-1082 acetochlor B-12 B-1083 cafenstrole B-12 B-1084 dimethenamid-P B-12 B-1085 fentrazamide B-12 B-1086 flufenacet B-12 B-1087 mefenacet B-12 B-1088 metazachlor B-12 B-1089 metolachlor-S B-12 B-1090 pyroxasulfone B-12 B-1091 isoxaben B-12 B-1092 dymron B-12 B-1093 indanofan B-12 B-1094 oxaziclomefone B-12 B-1095 triaziflam B-12 B-1096 atrazine + B-1 B-12 B-1097 atrazine + glyphosate B-12 B-1098 atrazine + mesotrione B-12 B-1099 atrazine + nicosulfuron B-12 B-1100 atrazine + tembotrione B-12 B-1101 atrazine + topramezone B-12 B-1102 clomazone + glyphosate B-12 B-1103 diflufenican + clodinafop-propargyl B-12 B-1104 diflufenican + fenoxaprop-P-ethyl B-12 B-1105 diflufenican + flupyrsulfuron-methyl-sodium B-12 B-1106 diflufenican + glyphosate B-12 B-1107 diflufenican + mesosulfuron-methyl B-12 B-1108 diflufenican + pinoxaden B-12 B-1109 diflufenican + pyroxsulam B-12 B-1110 flumetsulam + glyphosate B-12 B-1111 flumioxazin + glyphosate B-12 B-1112 imazapic + glyphosate B-12 B-1113 imazethapyr + glyphosate B-12 B-1114 isoxaflutol + B-1 B-12 B-1115 isoxaflutol + glyphosate B-12 B-1116 metazachlor + B-1 B-12 B-1117 metazachlor + glyphosate B-12 B-1118 metazachlor + mesotrione B-12 B-1119 metazachlor + nicosulfuron B-12 B-1120 metazachlor + terbuthylazin B-12 B-1121 metazachlor + topramezone B-12 B-1122 metribuzin + glyphosate B-12 B-1123 pendimethalin + B-1 B-12 B-1124 pendimethalin + clodinafop-propargyl B-12 B-1125 pendimethalin + fenoxaprop-P-ethyl B-12 B-1126 pendimethalin + flupyrsulfuron-methyl-sodium B-12 B-1127 pendimethalin + glyphosate B-12 B-1128 pendimethalin + mesosulfuron-methyl B-12 B-1129 pendimethalin + mesotrionee B-12 B-1130 pendimethalin + nicosulfuron B-12 B-1131 pendimethalin + pinoxaden B-12 B-1132 pendimethalin + pyroxsulam B-12 B-1133 pendimethalin + tembotrione B-12 B-1134 pendimethalin + topramezone B-12 B-1135 pyroxasulfone + tembotrione B-12 B-1136 pyroxasulfone + topramezone B-12 B-1137 sulfentrazone + glyphosate B-12 B-1138 terbuthylazin + B-1 B-12 B-1139 terbuthylazin + foramsulfuron B-12 B-1140 terbuthylazin + glyphosate B-12 B-1141 terbuthylazin + mesotrione B-12 B-1142 terbuthylazin + nicosulfuron B-12 B-1143 terbuthylazin + tembotrione B-12 B-1144 terbuthylazin + topramezone B-12 B-1145 trifluralin + glyphosate B-12 B-1146 2-1 — B-1147 2-2 — B-1148 2-3 — B-1149 2-4 — B-1150 2-5 — B-1151 2-6 — B-1152 2-7 — B-1153 2-8 — B-1154 2-9 — B-1155 2-1 benoxacor B-1156 2-2 benoxacor B-1157 2-3 benoxacor B-1158 2-4 benoxacor B-1159 2-5 benoxacor B-1160 2-6 benoxacor B-1161 2-7 benoxacor B-1162 2-8 benoxacor B-1163 2-9 benoxacor B-1164 2-1 cloquintocet B-1165 2-2 cloquintocet B-1166 2-3 cloquintocet B-1167 2-4 cloquintocet B-1168 2-5 cloquintocet B-1169 2-6 cloquintocet B-1170 2-7 cloquintocet B-1171 2-8 cloquintocet B-1172 2-9 cloquintocet B-1173 2-1 cyprosulfamide B-1174 2-2 cyprosulfamide B-1175 2-3 cyprosulfamide B-1176 2-4 cyprosulfamide B-1177 2-5 cyprosulfamide B-1178 2-6 cyprosulfamide B-1179 2-7 cyprosulfamide B-1180 2-8 cyprosulfamide B-1181 2-9 cyprosulfamide B-1182 2-1 dichlormid B-1183 2-2 dichlormid B-1184 2-3 dichlormid B-1185 2-4 dichlormid B-1186 2-5 dichlormid B-1187 2-6 dichlormid B-1188 2-7 dichlormid B-1189 2-8 dichlormid B-1190 2-9 dichlormid B-1191 2-1 fenchlorazole B-1192 2-2 fenchlorazole B-1193 2-3 fenchlorazole B-1194 2-4 fenchlorazole B-1195 2-5 fenchlorazole B-1196 2-6 fenchlorazole B-1197 2-7 fenchlorazole B-1198 2-8 fenchlorazole B-1199 2-9 fenchlorazole B-1200 2-1 isoxadifen B-1201 2-2 isoxadifen B-1202 2-3 isoxadifen B-1203 2-4 isoxadifen B-1204 2-5 isoxadifen B-1205 2-6 isoxadifen B-1206 2-7 isoxadifen B-1207 2-8 isoxadifen B-1208 2-9 isoxadifen B-1209 2-1 mefenpyr B-1210 2-2 mefenpyr B-1211 2-3 mefenpyr B-1212 2-4 mefenpyr B-1213 2-5 mefenpyr B-1214 2-6 mefenpyr B-1215 2-7 mefenpyr B-1216 2-8 mefenpyr B-1217 2-9 mefenpyr B-1218 2-1 B-11 B-1219 2-2 B-11 B-1220 2-3 B-11 B-1221 2-4 B-11 B-1222 2-5 B-11 B-1223 2-6 B-11 B-1224 2-7 B-11 B-1225 2-8 B-11 B-1226 2-9 B-11 B-1227 2-1 B-12 B-1228 2-2 B-12 B-1229 2-3 B-12 B-1230 2-4 B-12 B-1231 2-5 B-12 B-1232 2-6 B-12 B-1233 2-7 B-12 B-1234 2-8 B-12 B-1235 2-9 B-12

The compounds I and the compositions according to the invention may also have a plant-strengthening action. Accordingly, they are suitable for mobilizing the defense system of the plants against attack by unwanted microorganisms, such as harmful fungi, but also viruses and bacteria. Plant-strengthening (resistance-inducing) substances are to be understood as meaning, in the present context, those substances which are capable of stimulating the defense system of treated plants in such a way that, when subsequently inoculated by unwanted microorganisms, the treated plants display a substantial degree of resistance to these microorganisms.

The compounds I can be employed for protecting plants against attack by unwanted microorganisms within a certain period of time after the treatment. The period of time within which their protection is effected generally extends from 1 to 28 days, preferably from 1 to 14 days, after the treatment of the plants with the compounds I, or, after treatment of the seed, for up to 9 months after sowing.

The compounds I and the compositions according to the invention are also suitable for increasing the harvest yield.

Moreover, they have reduced toxicity and are tolerated well by the plants.

Hereinbelow, the preparation of pyridine compounds of the formula I is illustrated by way of examples.

SYNTHESIS EXAMPLES

With appropriate modification of the starting materials, the procedures given in the synthesis examples below were used to obtain compounds of the formula I.

Example 1 Preparation of methyl 3-(3-hydroxypyridin-2-yl)-3-oxo-2-(2-trifluoro-methylphenyl)propionate (not according to the invention) Step 1: Methyl 3-(4-methoxybenzyloxy)pyridine-2-carboxylate

4 g of NaH were added to a solution of 15.2 g of methyl 3-hydroxypyridin-2-ylcarboxylate in 200 ml of DMF and stirred for 30 min at 20-25° C. 15.4 g of para-methoxybenzyl chloride were then added. The mixture was stirred at 40° C. for about 15 hours and then poured into water. After extraction with ethyl acetate, phase separation and washing of the combined organic phases with water and sat. NaCl solution, then drying and removing of the solvent, the residue was subjected to column chromatography. This gave 20 g of the title compound as a yellow oil.

Step 2: 3-(4-Methoxybenzyloxy)pyridine-2-carboxylic acid

A solution of 7 g of the ester from step 1 and 2.2 g of LiOH in 60 ml of methanol and 40 ml of water was stirred at 20-25° C. for about 15 hours. 100 ml of water and 7 ml of acetic acid were then added. The mixture was extracted with ethyl acetate. The combined organic phases were dried and freed from the solvent. This gave 5 g of the title compound as a yellowish solid.

Step 3: Pentafluorophenyl 3-(4-methoxybenzyloxy)pyridine-2-carboxylate

2.4 g of N,N′-diisopropylcarbodiimide were added dropwise to a solution of 5 g of the acid from step 2 and 3.5 g of pentafluorophenol in 100 ml of CH₂Cl₂. The mixture was stirred at 20-25° C. for about 1 hour and then washed with sat. NaCl solution and concentrated under reduced pressure. Purification of the residue by column chromatography (petroleum ether:ethyl acetate 5:1) gave 4.6 g of the title compound.

Step 4: Methyl 3-[3-(4-methoxybenzyloxy)pyridin-2-yl]-3-oxo-2-(2-trifluoromethyl-phenyl)propionate

0.74 g of potassium tert-butoxide was added to a solution of 1.2 g of the ester from step 3 in 10 ml of DMF. The mixture was stirred at 20-25° C. for about 30 min. A solution of 2.25 g of methyl (2-trifluoromethylphenyl)acetate in 5 ml of DMF was then added. After 30 min of stirring at 20-25° C., the reaction was terminated by addition of sat. NH₄Cl solution. The mixture was extracted with ethyl acetate. The combined organic phases were washed with sat. NaCl solution and then dried and freed from the solvent. Purification of the residue by column chromatography (petroleum ether:ethyl acetate 5:1) gave 0.23 g of the title compound.

Step 5: Methyl 3-(3-hydroxypyridin-2-yl)-3-oxo-2-(2-trifluoromethylphenyl)propionate

At 0° C., 1 ml of trifluoroacetic acid was added to 160 mg of the ester from step 4, and the reaction mixture was stirred at 0° C. for 20 min. Sat. NaHCO₃ solution was then added. Extraction with ethyl acetate, removal of the solvent under reduced pressure and preparative HPLC gave 83 mg of the ester.

¹H NMR (CDCl₃): δ 11.05 (brs, 1H); 8.26-8.24 (m, 1H); 7.73 (d, 1H); 7.61-7.58 (m, 2H); 7.48-7.34 (m, 3H); 6.64 (s, 1H); 3.76 (s, 3H).

Step 6: 8-Hydroxy-7-(2-trifluoromethylphenyl)pyrano[2,3-b]pyrazin-6-one

350 mg of step 5 were dissolved in 7 ml of DMSO/sat. sodium chloride solution. The mixture was stirred at 100° C. for 2 h. The reaction solution was then diluted with 70 ml of 2N HCl and extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate. Removal of the solvent under reduced pressure and purification by prep. HPLC gave 83 mg of the title compound.

¹H NMR (MeOD): δ 8.64-8.69 (m, 2H), 7.82 (d, 1H, J=8 Hz), 7.71 (t, 1H, J=8 Hz), 7.61 (t, 1H, J=8 Hz), 7.45 (d, 1H, J=8 Hz).

Use Examples

The herbicidal activity of the compounds of the formula I was demonstrated by the following greenhouse experiments:

The culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.

For the pre-emergence treatment, the active compounds, which had been suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the plants had rooted. This cover caused uniform germination of the test plants, unless this has been impaired by the active compounds.

For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and then treated with the active compounds which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment.

Depending on the species, the plants were kept at 10-25° C. or 20-35° C. The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.

Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the aerial moieties, and 0 means no damage, or normal course of growth. A good herbicidal activity is given at values of at least 70 and a very good herbicidal activity is given at values of at least 85.

The plants used in the greenhouse experiments belonged to the following species:

Bayer code Scientific name Common name ABUTH Abutilon theophrasti China jute AVEFA Avena fatua spring wild-oat SETFA Setaria faberi giant foxtail SETIT Setaria italica Foxtail millet

1) At an application rate of 3.0 kg/ha, the active compound from example 1, applied by the pre-emergence method, showed very good herbicidal activity against SETIT.

2) At an application rate of 3.0 kg/ha, the active compound from example 1, applied by the post-emergence method, showed good herbicidal activity against ABUTH, AVEFA and SETFA. 

1-14. (canceled)
 15. A compound of formula (I)

in which R¹ is O—R^(A), or S(O)_(n)—R^(A) or OS(O)_(n)—R^(A); R^(A) is hydrogen, C₁-C₄-alkyl, Z—C₃-C₆-cycloalkyl, C₁-C₄-haloalkyl, C₂-C₆-alkenyl, Z—C₃-C₆-cycloalkenyl, C₂-C₆-alkynyl, Z-(tri-C₁-C₄-alkyl)silyl, Z—C(═O)—R^(a), Z—P(═O)(R^(a))₂, a 3- to 7-membered monocyclic or 9- or 10-membered bicyclic saturated, unsaturated or aromatic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, which may be partially or fully substituted by groups R^(a) and/or R^(b) and which is attached via carbon or nitrogen, R^(a) is hydrogen, OH, C₁-C₈-alkyl, C₁-C₄-haloalkyl, Z—C₃-C₆-cycloalkyl, C₂-C₈-alkenyl, Z—C₅-C₆-cycloalkenyl, C₂-C₈-alkynyl, Z—C₁-C₆-alkoxy, Z—C₁-C₄-haloalkoxy, Z—C₃-C₈-alkenyloxy, Z—C₃-C₈-alkynyloxy, NR^(i)R^(ii), C₁-C₆-alkylsulfonyl, Z-(tri-C₁-C₄-alkyl)silyl, Z-phenyl, Z-phenoxy, Z-phenylamino or a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, wherein the cyclic groups are unsubstituted or substituted by 1, 2, 3 or 4 groups R^(b); R^(i), R^(ii) independently of one another are hydrogen, C₁-C₈-alkyl, C₁-C₄-haloalkyl, C₃-C₈-alkenyl, C₃-C₈-alkynyl, Z—C₃-C₆-cycloalkyl, Z—C₁-C₈-alkoxy, or Z—C₁-C₈-haloalkoxy; or R^(i) and R^(ii) together with the nitrogen atom to which they are attached may form a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S; Z is a covalent bond or C₁-C₄-alkylene; n is 0, 1 or 2; R² is phenyl, naphthyl or a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic aromatic heterocycle which contains 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, wherein the cyclic groups are unsubstituted or substituted by 1, 2, 3 or 4 groups R^(b); R^(b) independently of one another are Z—CN, Z—OH, Z—NO₂, Z-halogen, C₁-C₈-alkyl, C₁-C₄-haloalkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, Z—C₁-C₈-alkoxy, Z—C₁-C₈-haloalkoxy, Z—C₃-C₁₀-cycloalkyl, O—Z—C₃-C₁₀-cycloalkyl, Z—C(═O)—R^(a), NR^(i)R^(ii), Z-(tri-C₁-C₄-alkyl)silyl, Z-phenyl and S(O)_(n)R^(bb), where R^(bb) is C₁-C₈-alkyl or C₁-C₆-haloalkyl and n is 0, 1 or 2; R^(b1), R^(b2) are one of the groups mentioned for R^(b); or one of R^(b), R^(b1), or R^(b2) independently of one another together with the group R^(b), R^(b1) or R^(b2) attached to an adjacent carbon atom may form a five- or six-membered saturated or partially or fully unsaturated ring which, in addition to carbon atoms, may contain 1, 2 or 3 heteroatoms selected from the group consisting of O, N and S; X is O, S or N—R³; R³ is hydrogen, C₁-C₆-alkyl, C₁-C₄-haloalkyl, C₂-C₆-alkenyl, C₃-C₆-alkynyl, Z-C₃-C₁₀-cycloalkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-cyanoalkyl, Z-phenyl, Z—C(═O)—R^(a2) or tri-C₁-C₄-alkylsilyl; R^(a2) is C₁-C₆-alkyl, C₁-C₄-haloalkyl, Z—C₁-C₆-alkoxy, Z—C₁-C₄-haloalkoxy or NR^(i)R^(ii); where in the groups R^(A), R², R³ and their subsubtituents, the carbon chains and/or the cyclic groups may be partially or fully substituted by groups R^(a), or a N-oxide or an agriculturally suitable salt thereof; with the proviso that R¹ is not OR^(A) or OS(O)_(n)—R^(A) when X is O.
 16. The compound of claim 15 in which R¹ is S(O), —R^(A).
 17. The compound of claim 15 in which R¹ is OR^(A) or OS(O)_(n)—R^(A).
 18. The compound of claim 15 in which R^(A) is H or C₁-C₆-alkylcarbonyl.
 19. The compound of claim 15 in which X is O.
 20. The compound of claim 15 in which X is S.
 21. The compound of claim 15 in which R³ is C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl-C₁-C₄-alkyl, C₃-C₆-alkenyl, optionally substituted phenyl, or S(O), —R^(N); and R^(N) is C₁-C₆-haloalkyl.
 22. The compound of claim 15 which corresponds to the compound of formula (I.A)

in which R⁵ and R⁶ are groups R^(b) and n is an integer from zero to four.
 23. The compound of claim 22 in which R⁵ is C₁-C₂-haloalkyl.
 24. The compound of claim 15 in which the substituents R^(b) are selected from the group consisting of halogen, NO₂, C₁-C₂-haloalkyl and C₁-C₄-alkoxy.
 25. A composition comprising a herbicidally effective amount of at least one compound of claim 15, or an agriculturally suitable salt thereof, and auxiliaries customary for formulating crop protection agents.
 26. The composition according to claim 25 which comprises at least one further active compound.
 27. The composition according to claim 26 which comprises two further active compounds from the group of the herbicides and/or safeners.
 28. A method for controlling unwanted vegetation which comprises allowing a herbicidally effective amount of at least one compound of claim 15, or an agriculturally suitable salt thereof, to act on plants, their seed and/or their habitat.
 29. The method of claim 28, wherein R¹ of the compound is S(O)_(n)—R^(A).
 30. The method of claim 28, wherein R¹ of the compound is OR^(A) or OS(O)_(n)—R^(A).
 31. The method of claim 28, wherein R^(A) of the compound is H or C₁-C₆-alkylcarbonyl.
 32. The method of claim 28, wherein X of the compound is O.
 33. The method of claim 28, wherein X of the compound is S.
 34. The method of claim 28, wherein the compound corresponds to the compound of formula (I.A)

in which R⁵ and R⁶ are groups R^(b) and n is an integer from zero to four. 